Light-emitting element, light-emitting device, electronic device, and lighting device

ABSTRACT

A novel organometallic complex with high reliability is provided. A light-emitting element includes an EL layer between a pair of electrodes. The EL layer includes at least a light-emitting layer. The light-emitting layer contains an organometallic complex. The organometallic complex includes a first ligand and a second ligand which are coordinated to a central metal. The HOMO is distributed over the first ligand, and the LUMO is distributed over the second ligand. The first ligand and the second ligand are cyclometalated ligands.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. application Ser. No. 15/471,017, filed Mar. 28, 2017, now pending, which claims the benefit of a foreign priority application filed in Japan as Serial No. 2016-074489 on Apr. 1, 2016, both of which are incorporated by reference.

TECHNICAL FIELD

One embodiment of the present invention relates to a light-emitting element, a light-emitting device, an electronic device, and a lighting device in which an organometallic complex is used. Note that one embodiment of the present invention is not limited to the above technical field. The technical field of one embodiment of the invention disclosed in this specification and the like relates to an object, a method, or a manufacturing method. One embodiment of the present invention relates to a process, a machine, manufacture, a substance (an organometallic complex), or a composition of matter. Specifically, other examples of the technical field of one embodiment of the present invention disclosed in this specification include a semiconductor device, a display device, a liquid crystal display device, a memory device, a method for driving any of them, and a method for manufacturing any of them.

BACKGROUND ART

A light-emitting element having a structure in which an organic compound that is a light-emitting substance is provided between a pair of electrodes (also referred to as an organic EL element) has characteristics such as thinness, light weight, high-speed response, and low voltage driving, and a display including such a light-emitting element has attracted attention as a next-generation flat panel display. When a voltage is applied to this light-emitting element, electrons and holes injected from the electrodes recombine to put the light-emitting substance into an excited state, and then light is emitted in returning from the excited state to the ground state. The excited state can be a singlet excited state (S*) and a triplet excited state (T*). Light emission from a singlet excited state is referred to as fluorescence, and light emission from a triplet excited state is referred to as phosphorescence. The statistical generation ratio thereof in the light-emitting element is considered to be S*:T*=1:3.

As the above light-emitting substance, a compound capable of converting singlet excitation energy into light emission is called a fluorescent compound (fluorescent material), and a compound capable of converting triplet excitation energy into light emission is called a phosphorescent compound (phosphorescent material).

Accordingly, on the basis of the above generation ratio, the internal quantum efficiency (the ratio of the number of generated photons to the number of injected carriers) of a light-emitting element including a fluorescent material is thought to have a theoretical limit of 25%, while the internal quantum efficiency of a light-emitting element including a phosphorescent material is thought to have a theoretical limit of 75%.

In other words, a light-emitting element including a phosphorescent material has higher efficiency than a light-emitting element including a fluorescent material. Thus, various kinds of phosphorescent materials have been actively developed in recent years. An organometallic complex that contains iridium or the like as a central metal is particularly attracting attention because of its high phosphorescence quantum yield (see Patent Document 1, for example).

Patent Document

[Patent Document 1] Japanese Published Patent Application No. 2009-23938

DISCLOSURE OF INVENTION

Although phosphorescent materials exhibiting excellent characteristics have been actively developed as disclosed in Patent Document 1, development of novel materials with better characteristics has been desired.

In view of the above, according to one embodiment of the present invention, a novel light-emitting element having high reliability is provided. According to one embodiment of the present invention, a novel organometallic complex that can be used in a light-emitting element is provided. According to one embodiment of the present invention, a novel organometallic complex that can be used in an EL layer of a light-emitting element is provided. According to one embodiment of the present invention, a novel light-emitting device, a novel electronic device, or a novel lighting device is provided. Note that the description of these objects does not disturb the existence of other objects. In one embodiment of the present invention, there is no need to achieve all the objects. Other objects will be apparent from and can be derived from the description of the specification, the drawings, the claims, and the like.

One embodiment of the present invention is a light-emitting element including an EL layer between a pair of electrodes. The EL layer includes at least a light-emitting layer. The light-emitting layer contains an organometallic complex. The organometallic complex includes a first ligand and a second ligand which are coordinated to a central metal. The first ligand has the HOMO, and the second ligand has the LUMO. The first ligand and the second ligand are cyclometalated ligands.

One embodiment of the present invention is a light-emitting element including an EL layer between a pair of electrodes. The EL layer includes at least a light-emitting layer. The light-emitting layer contains an organometallic complex. The organometallic complex includes a first ligand and a second ligand which are coordinated to a central metal. The HOMO is distributed over the first ligand, and the LUMO is distributed over the second ligand. The first ligand and the second ligand are cyclometalated ligands.

In the above embodiment, a first heteroaromatic ring coordinated to the central metal and included in the first ligand is different from a second heteroaromatic ring coordinated to the central metal and included in the second ligand.

In the above embodiment, the first heteroaromatic ring includes a first monocyclic ring containing a nitrogen atom coordinated to the central metal, the second heteroaromatic ring includes a second monocyclic ring containing a nitrogen atom coordinated to the central metal, and the first monocyclic ring is different from the second monocyclic ring.

In the above embodiment, the number of members in each of the first monocyclic ring and the second monocyclic ring is 5 or 6.

In the above embodiment, the number of the nitrogen atom in the first monocyclic ring is 1, and the number of the nitrogen atom in the second monocyclic ring is 2 or 3.

In the above embodiment, the first monocyclic ring is a pyridine ring, and the second monocyclic ring is a pyrimidine ring or a triazine ring.

In the above embodiment, the first heteroaromatic ring is a pyridine ring, and the second heteroaromatic ring is a pyrimidine ring or a triazine ring.

In the above embodiment, the central metal is preferably iridium. In that case, since iridium is trivalent, the total number of the first and second ligands in the organometallic complex is preferably 3. At that time, it is preferable that the number of the first ligand over which the HOMO is distributed be 2 and the number of the second ligand over which the LUMO is distributed be 1.

Another embodiment of the present invention is an organometallic complex having a structure represented by General Formula (G1) below.

In General Formula (G1), R¹ to R¹⁵ separately represent hydrogen, a halogen group, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted aryl group having 6 to 13 carbon atoms, or a substituted or unsubstituted heteroaryl group having 3 to 12 carbon atoms.

Another embodiment of the present invention is an organometallic complex having a structure represented by General Formula (G2) below.

In General Formula (G2), n is 1 or 2. R¹ to R¹⁵ separately represent hydrogen, a halogen group, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted aryl group having 6 to 13 carbon atoms, or a substituted or unsubstituted heteroaryl group having 3 to 12 carbon atoms.

The organometallic complex used in the light-emitting element of one embodiment of the present invention has a shallow HOMO and a deep LUMO as a whole because the HOMO and the LUMO are spatially separated from each other by being distributed over different ligands. Thus, the use of such an organometallic complex improves carrier-injection and carrier-transport properties with respect to both electrons and holes. Therefore, the use thereof as a light-emitting material in the light-emitting element decreases drive voltage and increases efficiency. In addition, in the organometallic complex used in the light-emitting element of one embodiment of the present invention, both at the time of carrier transport and in an excited state, holes are distributed over a ligand that is highly resistant to holes (the first ligand over which the HOMO is likely to be distributed), and electrons are distributed over a ligand that is highly resistant to electrons (the second ligand over which the LUMO is likely to be distributed). This makes it possible to increase stability at the time of carrier transport and in an excited state and to manufacture a light-emitting element with long lifetime. Furthermore, by such separation of the HOMO and the LUMO from each other, the organometallic complex itself can transport both carriers; thus, carrier balance can be adjusted. This also contributes to an increase of lifetime.

One embodiment of the present invention includes, in its scope, not only a light-emitting device including the light-emitting element but also a lighting device including the light-emitting device. The light-emitting device in this specification refers to an image display device and a light source (e.g., a lighting device). In addition, the light-emitting device includes, in its category, all of a module in which a connector such as a flexible printed circuit (FPC) or a tape carrier package (TCP) is connected to a light-emitting device, a module in which a printed wiring board is provided on the tip of a TCP, and a module in which an integrated circuit (IC) is directly mounted on a light-emitting element by a chip on glass (COG) method.

According to one embodiment of the present invention, a novel light-emitting element having high reliability can be provided. According to one embodiment of the present invention, a novel organometallic complex that can be used in a light-emitting element can be provided. According to one embodiment of the present invention, a novel light-emitting device, a novel electronic device, or a novel lighting device can be provided.

BRIEF DESCRIPTION OF DRAWINGS

FIGS. 1A and 1B illustrate structures of light-emitting elements.

FIGS. 2A and 2B illustrate structures of light-emitting elements.

FIGS. 3A to 3C illustrate light-emitting devices.

FIGS. 4A and 4B illustrate a light-emitting device.

FIGS. 5A, 5B, 5C, 5D, 5D′-1, and 5D′-2 illustrate electronic devices.

FIGS. 6A to 6C illustrate an electronic device.

FIGS. 7A and 7B illustrate an automobile.

FIGS. 8A to 8D illustrate lighting devices.

FIG. 9 illustrates lighting devices.

FIGS. 10A and 10B illustrate an example of a touch panel.

FIGS. 11A and 11B illustrate an example of a touch panel.

FIGS. 12A and 12B illustrate an example of a touch panel.

FIGS. 13A and 13B are a block diagram and a timing chart of a touch sensor.

FIG. 14 is a circuit diagram of a touch sensor.

FIGS. 15A, 15B1, and 15B2 illustrate block diagrams of display devices.

FIG. 16 illustrates a circuit configuration of a display device.

FIG. 17 illustrates a cross-sectional structure of a display device.

FIGS. 18A and 18B illustrate a light-emitting element.

FIG. 19 is a ¹H-NMR chart of an organometallic complex represented by Structural Formula (100).

FIG. 20 shows an ultraviolet-visible absorption spectrum and an emission spectrum of the organometallic complex represented by Structural Formula (100).

FIG. 21 shows results of LC-MS measurement of the organometallic complex represented by Structural Formula (100).

FIG. 22 shows a ¹H-NMR chart of an organometallic complex represented by Structural Formula (102).

FIG. 23 shows an ultraviolet-visible absorption spectrum and an emission spectrum of the organometallic complex represented by Structural Formula (102).

FIG. 24 shows results of LC-MS measurement of the organometallic complex represented by Structural Formula (102).

FIG. 25 shows a ¹H-NMR chart of an organometallic complex represented by Structural Formula (114).

FIG. 26 shows an ultraviolet-visible absorption spectrum and an emission spectrum of the organometallic complex represented by Structural Formula (114).

FIG. 27 shows results of LC-MS measurement of the organometallic complex represented by Structural Formula (114).

FIG. 28 shows a ¹H-NMR chart of an organometallic complex represented by Structural Formula (120).

FIG. 29 shows an ultraviolet-visible absorption spectrum and an emission spectrum of the organometallic complex represented by Structural Formula (120).

FIG. 30 shows results of LC-MS measurement of the organometallic complex represented by Structural Formula (120).

FIG. 31 illustrates a light-emitting element.

FIG. 32 shows current density-luminance characteristics of light-emitting elements.

FIG. 33 shows voltage-luminance characteristics of the light-emitting elements.

FIG. 34 shows luminance-current efficiency characteristics of the light-emitting elements.

FIG. 35 shows voltage-current characteristics of the light-emitting elements.

FIG. 36 shows emission spectra of the light-emitting elements.

FIG. 37 shows reliability of the light-emitting elements.

FIG. 38 shows current density-luminance characteristics of a light-emitting element.

FIG. 39 shows voltage-luminance characteristics of the light-emitting element.

FIG. 40 shows luminance-current efficiency characteristics of the light-emitting element.

FIG. 41 shows voltage-current characteristics of the light-emitting element.

FIG. 42 shows an emission spectrum of the light-emitting element.

FIG. 43 shows a ¹H-NMR chart of an organometallic complex represented by Structural Formula (117).

FIG. 44 shows an ultraviolet-visible absorption spectrum and an emission spectrum of the organometallic complex represented by Structural Formula (117).

FIG. 45 shows results of LC-MS measurement of the organometallic complex represented by Structural Formula (117).

FIG. 46 shows a ¹H-NMR chart of an organometallic complex represented by Structural Formula (200).

FIG. 47 shows an ultraviolet-visible absorption spectrum and an emission spectrum of the organometallic complex represented by Structural Formula (200).

FIG. 48 shows results of LC-MS measurement of the organometallic complex represented by Structural Formula (200).

FIG. 49 shows a ¹H-NMR chart of an organometallic complex represented by Structural Formula (300).

FIG. 50 shows an ultraviolet-visible absorption spectrum and an emission spectrum of the organometallic complex represented by Structural Formula (300).

FIG. 51 shows results of LC-MS measurement of the organometallic complex represented by Structural Formula (300).

FIG. 52 shows a ¹H-NMR chart of an organometallic complex represented by Structural Formula (118).

FIG. 53 shows an ultraviolet-visible absorption spectrum and an emission spectrum of the organometallic complex represented by Structural Formula (118).

FIG. 54 shows a ¹H-NMR chart of an organometallic complex represented by Structural Formula (119).

FIG. 55 shows an ultraviolet-visible absorption spectrum and an emission spectrum of the organometallic complex represented by Structural Formula (119).

FIG. 56 shows results of LC-MS measurement of the organometallic complex represented by Structural Formula (119).

FIG. 57 shows current density-luminance characteristics of light-emitting elements.

FIG. 58 shows voltage-luminance characteristics of the light-emitting elements.

FIG. 59 shows luminance-current efficiency characteristics of the light-emitting elements.

FIG. 60 shows voltage-current characteristics of the light-emitting elements.

FIG. 61 shows emission spectra of the light-emitting elements.

FIG. 62 shows reliability of the light-emitting elements.

FIG. 63 shows current density-luminance characteristics of light-emitting elements.

FIG. 64 shows voltage-luminance characteristics of the light-emitting elements.

FIG. 65 shows luminance-current efficiency characteristics of the light-emitting elements.

FIG. 66 shows voltage-current characteristics of the light-emitting elements.

FIG. 67 shows emission spectra of the light-emitting elements.

FIG. 68 shows reliability of the light-emitting elements.

BEST MODE FOR CARRYING OUT THE INVENTION

Embodiments of the present invention will be described below with reference to the drawings. Note that the present invention is not limited to the following description, and the modes and details of the present invention can be modified in various ways without departing from the spirit and scope of the present invention. Therefore, the present invention should not be construed as being limited to the description in the following embodiments.

Note that the terms “film” and “layer” can be interchanged with each other depending on the case or circumstances. For example, the term “conductive layer” can be changed into the term “conductive film” in some cases. Also, the term “insulating film” can be changed into the term “insulating layer” in some cases.

Embodiment 1

In this embodiment, a light-emitting element of one embodiment of the present invention is described with reference to FIGS. 1A and 1B.

In the light-emitting element described in this embodiment, an EL layer 102 including a light-emitting layer 113 is provided between a pair of electrodes (a first electrode (anode) 101 and a second electrode (cathode) 103), and the EL layer 102 includes a hole-injection layer 111, a hole-transport layer 112, an electron-transport layer 114, an electron-injection layer 115, and the like in addition to the light-emitting layer 113. Note that the light-emitting layer 113 contains a light-emitting substance.

When a voltage is applied to the light-emitting element, holes injected from the first electrode 101 side and electrons injected from the second electrode 103 side recombine in the light-emitting layer 113; with energy generated by the recombination, the light-emitting substance such as an organometallic complex that is contained in the light-emitting layer 113 emits light.

The light-emitting layer 113 preferably contains a host material and a guest material that is the light-emitting substance. In that case, in the light-emitting layer 113, the host material is present in the largest proportion by weight, and the guest material is dispersed in the host material. Note that a substance that has a higher triplet excitation energy level than that of the guest material is preferably used as the host material.

In a light-emitting element of one embodiment of the present invention, an organometallic complex is preferably used, and an organometallic complex of one embodiment of the present invention is further preferably used, as a light-emitting substance in a light-emitting layer included in an EL layer. The organometallic complex of one embodiment of the present invention includes a first ligand and a second ligand which are coordinated to a central metal. The highest occupied molecular orbital (HOMO) is distributed over the first ligand, and the lowest unoccupied molecular orbital (LUMO) is distributed over the second ligand. The first ligand and the second ligand are cyclometalated ligands. Note that the central metal is preferably iridium, platinum, or the like.

As a method for distributing the HOMO over the first ligand and the LUMO over the second ligand, a first heteroaromatic ring coordinated to the central metal and included in the first ligand is preferably different from a second heteroaromatic ring coordinated to the central metal and included in the second ligand. However, one embodiment of the present invention is not necessarily limited to this method as long as the HOMO is distributed over the first ligand and the LUMO is distributed over the second ligand. Note that examples of the first heteroaromatic ring included in the first ligand over which the HOMO is likely to be distributed include a pyridine ring, a quinoline ring, an isoquinoline ring, an imidazole ring, a benzimidazole ring, and the like, and examples of the second heteroaromatic ring included in the second ligand over which the LUMO is likely to be distributed include a pyridazine ring, a pyrimidine ring, a pyrazine ring, a triazine ring, a cinnoline ring, a phthalazine ring, a quinazoline ring, a quinoxaline ring, and the like.

It is important in separating the HOMO and the LUMO as described above that portions of the first heteroaromatic ring and the second heteroaromatic ring which are coordinated to the central metal have different ring structures. In other words, in the case where a nitrogen atom is coordinated to the central metal, it is important that a monocyclic ring structure containing the nitrogen atom is different between the first heteroaromatic ring and the second heteroaromatic ring. Therefore, in one embodiment of the present invention, the first heteroaromatic ring includes a first monocyclic ring containing a nitrogen atom coordinated to the central metal, the second heteroaromatic ring includes a second monocyclic ring containing a nitrogen atom coordinated to the central metal, and the first monocyclic ring is different from the second monocyclic ring. For example, in the case where the first heteroaromatic ring included in the first ligand is quinoline and a nitrogen atom of quinoline is coordinated to the central metal, the first monocyclic ring refers to a pyridine ring. In the case where the second heteroaromatic ring included in the second ligand is quinoxaline and a nitrogen atom of quinoxaline is coordinated to the central metal, the second monocyclic ring refers to a pyrazine ring. In the case where the first heteroaromatic ring is a monocyclic ring, the first heteroaromatic ring and the first monocyclic ring are practically identical with each other. Similarly, in the case where the second heteroaromatic ring is a monocyclic ring, the second heteroaromatic ring and the second monocyclic ring are practically identical with each other. Such a structure makes it easier to separate the HOMO and the LUMO from each other. Note that the first monocyclic ring and the second monocyclic ring are each preferably a five-membered ring or a six-membered ring.

In the above structure, the number of nitrogen atoms in the first monocyclic ring is 1, and the number of nitrogen atoms in the second monocyclic ring is 2 or 3. As the number of nitrogen atoms increases, a nitrogen-containing heteroaromatic ring becomes more electron-deficient and has a lower HOMO and a lower LUMO. Therefore, the number of nitrogen atoms in pyridine or the first monocyclic ring is set to 1 and the number of nitrogen atoms in the second monocyclic ring is set to 2 or 3 so that the HOMO and the LUMO are more likely to be distributed over the first ligand and the second ligand, respectively. From such a point of view, it is preferable that the first monocyclic ring be a pyridine ring and the second monocyclic ring be a pyrimidine ring or a triazine ring. In the case where the first monocyclic ring is a pyridine ring, the first heteroaromatic ring is preferably a pyridine ring, a quinoline ring, or an isoquinoline ring, and in the case where the second monocyclic ring is a pyrimidine ring or a triazine ring, the second heteroaromatic ring is preferably a pyrimidine ring, a triazine ring, or a quinazoline ring.

In the above structure, the first heteroaromatic ring and the second heteroaromatic ring are each preferably a monocyclic ring in terms of sublimability. In other words, it is preferable that the first heteroaromatic ring be a pyridine ring and the second heteroaromatic ring be a pyrimidine ring or a triazine ring.

In the case where the central metal is iridium in the above structure, since iridium is trivalent, the total number of the first and second ligands in the organometallic complex is preferably 3. With such a structure, the organometallic complex can include only the first and second ligands as its ligands. This allows the HOMO and the LUMO to be more likely to be distributed over the first ligand and the second ligand, respectively. At that time, it is preferable that the number of the first ligand over which the HOMO is distributed be 2 and the number of the second ligand over which the LUMO is distributed be 1. The present inventors have found that such a structure has a particularly significant effect of increasing lifetime.

Note that the above-described organometallic complex is represented by General Formula (G1) or General Formula (G2) below. The organometallic complexes represented by General Formula (G1) and General Formula (G2) are included in one embodiment of the present invention.

In General Formula (G1), R¹ to R¹⁵ separately represent hydrogen, a halogen group, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted aryl group having 6 to 13 carbon atoms, or a substituted or unsubstituted heteroaryl group having 3 to 12 carbon atoms.

In General Formula (G2), n is 1 or 2. R¹ to R¹⁵ separately represent hydrogen, a halogen group, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted aryl group having 6 to 13 carbon atoms, or a substituted or unsubstituted heteroaryl group having 3 to 12 carbon atoms.

Specific examples of the alkyl group having 1 to 6 carbon atoms which is represented by any of R¹ to R¹⁵ in General Formulae (G1) and (G2) include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a sec-pentyl group, a tert-pentyl group, a neopentyl group, a hexyl group, an isohexyl group, a sec-hexyl group, a tert-hexyl group, a neohexyl group, a 3-methylpentyl group, a 2-methylpentyl group, a 2-ethylbutyl group, a 1,2-dimethylbutyl group, a 2,3-dimethylbutyl group, a trifluoromethyl group, and the like.

Specific examples of the aryl group having 6 to 13 carbon atoms which is represented by any of R¹ to R¹⁵ in General Formulae (G1) and (G2) include a phenyl group, a tolyl group (an o-tolyl group, an m-tolyl group, and a p-tolyl group), a naphthyl group (a 1-naphthyl group and a 2-naphthyl group), a biphenyl group (a biphenyl-2-yl group, a biphenyl-3-yl group, and a biphenyl-4-yl group), a xylyl group, a pentalenyl group, an indenyl group, a fluorenyl group, a phenanthryl group, and the like. Note that the above substituents may be bonded to each other to form a ring. In such a case, for example, a spirofluorene skeleton is formed in such a manner that carbon at the 9-position of a fluorenyl group has two phenyl groups as substituents and these phenyl groups are bonded to each other.

Specific examples of the heteroaryl group having 3 to 12 carbon atoms which is represented by any of R¹ to R¹⁵ in General Formulae (G1) and (G2) include an imidazolyl group, a pyrazolyl group, a pyridyl group, a pyridazyl group, a triazyl group, a benzimidazolyl group, a quinolyl group, a carbazolyl group, a dibenzofuranyl group, a dibenzothiophenyl group, and the like.

In each of General Formulae (G1) and (G2), when any of the substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, the substituted or unsubstituted aryl group having 6 to 13 carbon atoms, and the substituted or unsubstituted heteroaryl group having 3 to 12 carbon atoms has a substituent, examples of the substituent include an alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, or a hexyl group; a cycloalkyl group having 5 to 7 carbon atoms, such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a 1-norbornyl group, or a 2-norbornyl group; and an aryl group having 6 to 12 carbon atoms, such as a phenyl group or a biphenyl group. The above substituents may be bonded to each other to form a ring. In such a case, for example, a spirofluorene skeleton is formed in such a manner that any of R¹ to R¹⁵ is a fluorenyl group that is an aryl group having 13 carbon atoms, carbon at the 9-position of the fluorenyl group has two phenyl groups as substituents, and these phenyl groups are bonded to each other.

An organometallic complex represented by any of Structural Formulae (100) to (116), (200), (201), (300), and (301) below can also be used in the light-emitting element of one embodiment of the present invention.

Note that the use of any of the above organometallic complexes in the light-emitting layer 113 of the light-emitting element enables the light-emitting element to achieve low drive voltage, high emission efficiency, long lifetime, and high reliability.

The above organometallic complex has a shallow HOMO and a deep LUMO as a whole because the HOMO and the LUMO are spatially separated from each other by being distributed over different ligands. The use of such an organometallic complex improves carrier-injection and carrier-transport properties with respect to both electrons and holes. Therefore, the use thereof as a light-emitting material in the light-emitting element decreases drive voltage and increases efficiency. In addition, in the organometallic complex used in the light-emitting element of one embodiment of the present invention, both at the time of carrier transport and in an excited state, holes are distributed over a ligand that is highly resistant to holes (the first ligand over which the HOMO is likely to be distributed), and electrons are distributed over a ligand that is highly resistant to electrons (the second ligand over which the LUMO is likely to be distributed). This makes it possible to increase stability at the time of carrier transport and in an excited state and to manufacture a light-emitting element with long lifetime. Furthermore, by such separation of the HOMO and the LUMO from each other, the organometallic complex itself can transport both carriers; thus, carrier balance can be adjusted. This also contributes to an increase of lifetime.

In the case where an organometallic complex including only the first ligand has a first driving lifetime and an organometallic complex including only the second ligand has a second driving lifetime, the lifetime of an organometallic complex including a combination of the first and second ligands is normally expected to be limited by the first driving lifetime or the second driving lifetime, whichever is shorter, or expected to be between the first driving lifetime and the second driving lifetime. However, as described in one embodiment of the present invention, separation of the HOMO and the LUMO from each other owing to the combination of the first and second ligands further makes the lifetime longer than the first driving lifetime and the second driving lifetime. This surprising phenomenon has been newly found by the present inventors.

The organometallic complexes represented by the above structural formulae are novel substances capable of emitting phosphorescence. There can be geometrical isomers and stereoisomers of these substances depending on the type of the ligand. Each of the isomers is also an organometallic complex of one embodiment of the present invention.

Next, an example of a method for synthesizing the organometallic complex represented by General Formula (G1) is described.

<<Method for Synthesizing Organometallic Complex Represented by General Formula (G1)>>

The organometallic complex that is one embodiment of the present invention and represented by General Formula (G1) can be obtained by reacting a dinuclear complex (P1) having a halogen-bridged structure with a pyridine compound represented by General Formula (G0-a) in an inert gas atmosphere, as shown in Synthesis Scheme (A) below.

In Synthesis Scheme (A), X represents a halogen atom, and R¹ to R¹⁵ separately represent hydrogen, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted aryl group having 6 to 13 carbon atoms, or a substituted or unsubstituted heteroaryl group having 3 to 12 carbon atoms.

The organometallic complex that is obtained under Synthesis Scheme (A) may be irradiated with light or heat to be further reacted, in which case an isomer such as a geometrical isomer or an optical isomer can be obtained. This isomer is also the organometallic complex represented by General Formula (G1). After the dinuclear complex (P1) having a halogen-bridged structure is reacted with an antichlor such as silver trifluoromethanesulfonate to precipitate silver chloride, a supernatant liquid may be reacted with the pyridine compound represented by General Formula (G0-a) in an inert gas atmosphere.

Next, an example of a method for synthesizing an organometallic complex represented by General Formula (G2-a) is described.

<<Method for Synthesizing Organometallic Complex Represented by General Formula (G2-a)>>

The organometallic complex that is one embodiment of the present invention and represented by General Formula (G2-a) can be obtained by reacting a dinuclear complex (P2) having a halogen-bridged structure with the pyridine compound represented by General Formula (G0-a) in an inert gas atmosphere, as shown in Synthesis Scheme (B) below.

Note that in Synthesis Scheme (B), X represents a halogen atom, and R¹ to R¹⁵ separately represent hydrogen, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted aryl group having 6 to 13 carbon atoms, or a substituted or unsubstituted heteroaryl group having 3 to 12 carbon atoms.

The organometallic complex that is obtained under Synthesis Scheme (B) may be irradiated with light or heat to be further reacted, in which case an isomer such as a geometrical isomer or an optical isomer can be obtained. This isomer is also the organometallic complex represented by General Formula (G2-a). After the dinuclear complex (P2) having a halogen-bridged structure is reacted with an antichlor such as silver trifluoromethanesulfonate to precipitate silver chloride, a supernatant liquid may be reacted with the pyridine compound represented by General Formula (G0-a) in an inert gas atmosphere.

Next, an example of a method for synthesizing an organometallic complex represented by General Formula (G2-b) below is described.

<<Method for Synthesizing Organometallic Complex Represented by General Formula (G2-b)>>

The organometallic complex that is one embodiment of the present invention and represented by General Formula (G2-a) can be obtained by reacting a dinuclear complex (P3) having a halogen-bridged structure with a triazine compound represented by General Formula (G0-b) in an inert gas atmosphere, as shown in Synthesis Scheme (C) below.

In Synthesis Scheme (C), X represents a halogen atom, and R¹ to R¹⁵ separately represent hydrogen, a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted aryl group having 6 to 13 carbon atoms, or a substituted or unsubstituted heteroaryl group having 3 to 12 carbon atoms.

The organometallic complex that is obtained under Synthesis Scheme (C) may be irradiated with light or heat to be further reacted, in which case an isomer such as a geometrical isomer or an optical isomer can be obtained. This isomer is also the organometallic complex represented by General Formula (G2-b). After the dinuclear complex (P3) having a halogen-bridged structure is reacted with an antichlor such as silver trifluoromethanesulfonate to precipitate silver chloride, a supernatant liquid may be reacted with the triazine compound represented by General Formula (G0-b) in an inert gas atmosphere.

In the above-described organometallic complex of one embodiment of the present invention, a substituent is preferably bonded to R⁶ of the pyrimidine or triazine compound in order that an ortho-metalated complex containing, as a ligand, the pyrimidine or triazine compound can be obtained. As R⁶, it is particularly preferable to use a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a substituted or unsubstituted aryl group having 6 to 13 carbon atoms, or a substituted or unsubstituted heteroaryl group having 3 to 12 carbon atoms. In that case, decomposition of the halogen-bridged dinuclear metal complex during the reaction represented by Synthesis Scheme (A), (B), or (C) is more suppressed than in the case where hydrogen is used as R⁶, leading to a drastically high yield.

The above is the description of examples of methods for synthesizing the organometallic complex used in the light-emitting element of one embodiment of the present invention; however, the present invention is not limited thereto, and any other synthesis methods may be employed.

The above-described organometallic complex can emit phosphorescence and thus can be used as a light-emitting material or a light-emitting substance of a light-emitting element.

With the use of the light-emitting element of one embodiment of the present invention, a light-emitting device, an electronic device, or a lighting device with long lifetime can be obtained.

In this embodiment, one embodiment of the present invention has been described. Other embodiments of the present invention are described in the other embodiments. Note that one embodiment of the present invention is not limited thereto. In other words, since various embodiments of the invention are described in this embodiment and the other embodiments, one embodiment of the present invention is not limited to a particular embodiment. For example, although an example of use in a light-emitting element is described in this embodiment, one embodiment of the present invention is not limited thereto. Depending on circumstances, one embodiment of the present invention may be used in objects other than a light-emitting element.

The structures described in this embodiment can be combined with any of the structures described in the other embodiments as appropriate.

Embodiment 2

In this embodiment, the light-emitting element that is described in Embodiment 1 and is one embodiment of the present invention is described in more detail. Note that the description is made with reference to FIGS. 1A and 1B as in Embodiment 1.

In the light-emitting element described in this embodiment, the EL layer 102 including the light-emitting layer 113 is provided between a pair of electrodes (the first electrode (anode) 101 and the second electrode (cathode) 103), and the EL layer 102 includes the hole-injection layer 111, the hole-transport layer 112, the electron-transport layer 114, the electron-injection layer 115, and the like in addition to the light-emitting layer 113.

The hole-injection layer 111 in the EL layer 102 can inject holes into the hole-transport layer 112 or the light-emitting layer 113 and can be formed of, for example, a substance having a high hole-transport property and a substance having an acceptor property, in which case electrons are extracted from the substance having a high hole-transport property by the substance having an acceptor property to generate holes. Thus, holes are injected from the hole-injection layer 111 into the light-emitting layer 113 through the hole-transport layer 112. For the hole-injection layer 111, a substance having a high hole-injection property can also be used. For example, molybdenum oxide, vanadium oxide, ruthenium oxide, tungsten oxide, manganese oxide, or the like can be used. Alternatively, the hole-injection layer 111 can be formed using a phthalocyanine-based compound such as phthalocyanine (abbreviation: H₂Pc) and copper phthalocyanine (CuPc), an aromatic amine compound such as 4,4′-bis[N-(4-diphenylaminophenyl)-N-phenylamino]biphenyl (abbreviation: DPAB) and N,N′-bis{4-[bis(3-methylphenyl)amino]phenyl}-N,N′-diphenyl-(1,1′-biphenyl)-4,4′-diamine (abbreviation: DNTPD), or a high molecular compound such as poly(3,4-ethylenedioxythiophene)/poly(styrenesulfonic acid) (PEDOT/PSS).

A preferred specific example in which the light-emitting element described in this embodiment is fabricated is described below.

For the first electrode (anode) 101 and the second electrode (cathode) 103, a metal, an alloy, an electrically conductive compound, a mixture thereof, and the like can be used. Specific examples include indium oxide-tin oxide (indium tin oxide), indium oxide-tin oxide containing silicon or silicon oxide, indium oxide-zinc oxide (indium zinc oxide), indium oxide containing tungsten oxide and zinc oxide, gold (Au), platinum (Pt), nickel (Ni), tungsten (W), chromium (Cr), molybdenum (Mo), iron (Fe), cobalt (Co), copper (Cu), palladium (Pd), and titanium (Ti). In addition, an element belonging to Group 1 or Group 2 of the periodic table, for example, an alkali metal such as lithium (Li) or cesium (Cs), an alkaline earth metal such as calcium (Ca) or strontium (Sr), magnesium (Mg), an alloy containing such an element (MgAg or AlLi), a rare earth metal such as europium (Eu) or ytterbium (Yb), an alloy containing such an element, graphene, and the like can be used. The first electrode (anode) 101 and the second electrode (cathode) 103 can be formed by, for example, a sputtering method or an evaporation method (including a vacuum evaporation method).

As the substance having a high hole-transport property which is used for the hole-injection layer 111 and the hole-transport layer 112, any of a variety of organic compounds such as aromatic amine compounds, carbazole derivatives, aromatic hydrocarbons, and high molecular compounds (e.g., oligomers, dendrimers, or polymers) can be used. An organic compound used for a composite material is preferably an organic compound having a high hole-transport property. Specifically, a substance having a hole mobility of 1×10⁻⁶ cm²/Vs or higher is preferably used. The layer formed using the substance having a high hole-transport property is not limited to a single layer and may be formed by stacking two or more layers. Organic compounds that can be used as the substance having a hole-transport property are specifically given below.

Examples of the aromatic amine compounds are N,N′-di(p-tolyl)-N,N′-diphenyl-p-phenylenediamine (abbreviation: DTDPPA), 4,4′-bis[N-(4-diphenylaminophenyl)-N-phenylamino]biphenyl (abbreviation: DPAB), DNTPD, 1,3,5-tris[N-(4-diphenylaminophenyl)-N-phenylamino]benzene (abbreviation: DPA3B), 4,4′-bis[N-(1-naphthyl)-N-phenylamino]biphenyl (abbreviation: NPB or α-NPD), N,N′-bis(3-methylphenyl)-N,N′-diphenyl-[1,1′-biphenyl]-4,4′-diamine (abbreviation: TPD), 4,4′,4″-tris(carbazol-9-yl)triphenylamine (abbreviation: TCTA), 4,4′,4″-tris(N,N-diphenylamino)triphenylamine (abbreviation: TDATA), 4,4′,4″-tris[N-(3-methylphenyl)-N-phenylamino]triphenylamine (abbreviation: MTDATA), 4,4′-bis[N-(spiro-9,9′-bifluoren-2-yl)-N-phenylamino]biphenyl (abbreviation: BSPB), and the like.

Specific examples of the carbazole derivatives are 3-[4N-(9-phenylcarbazol-3-yl)-N-phenylamino]-9-phenylcarbazole (abbreviation: PCzPCA1), 3,6-bis[N-(9-phenylcarbazol-3-yl)-N-phenylamino]-9-phenylcarbazole (abbreviation: PCzPCA2), 3-[N-(1-naphthyl)-N-(9-phenylcarbazol-3-yl)amino]-9-phenylcarbazole (abbreviation: PCzPCN1), and the like. Other examples are 4,4′-di(N-carbazolyl)biphenyl (abbreviation: CBP), 1,3,5-tris[4-(N-carbazolyl)phenyl]benzene (abbreviation: TCPB), 9-[4-(10-phenyl-9-anthryl)phenyl]-9H-carbazole (abbreviation: CzPA), 1,4-bis[4-(N-carbazolyl)phenyl]-2,3,5,6-tetraphenylbenzene, and the like.

Examples of the aromatic hydrocarbons are 2-tert-butyl-9,10-di(2-naphthyl)anthracene (abbreviation: t-BuDNA), 2-tert-butyl-9,10-di(1-naphthyl)anthracene, 9,10-bis(3,5-diphenylphenyl)anthracene (abbreviation: DPPA), 2-tert-butyl-9,10-bis(4-phenylphenyl)anthracene (abbreviation: t-BuDBA), 9,10-di(2-naphthyl)anthracene (abbreviation: DNA), 9,10-diphenylanthracene (abbreviation: DPAnth), 2-tert-butylanthracene (abbreviation: t-BuAnth), 9,10-bis(4-methyl-1-naphthyl)anthracene (abbreviation: DMNA), 2-tert-butyl-9,10-bis[2-(1-naphthyl)phenyl]anthracene, 9,10-bis[2-(1-naphthyl)phenyl]anthracene, 2,3,6,7-tetramethyl-9,10-di(1-naphthyl)anthracene, 2,3,6,7-tetramethyl-9,10-di(2-naphthyl)anthracene, 9,9′-bianthryl, 10,10′-diphenyl-9,9′-bianthryl, 10,10′-bis(2-phenylphenyl)-9,9′-bianthryl, 10,10′-bis[(2,3,4,5,6-pentaphenyl)phenyl]-9,9′-bianthryl, anthracene, tetracene, rubrene, perylene, 2,5,8,11-tetra(tert-butyl)perylene, and the like. Besides, pentacene, coronene, or the like can also be used. The aromatic hydrocarbon which has a hole mobility of 1×10⁻⁶ cm²/Vs or higher and which has 14 to 42 carbon atoms is particularly preferable. The aromatic hydrocarbons may have a vinyl skeleton. Examples of the aromatic hydrocarbon having a vinyl group are 4,4′-bis(2,2-diphenylvinyl)biphenyl (abbreviation: DPVBi), 9,10-bis[4-(2,2-diphenylvinyl)phenyl]anthracene (abbreviation: DPVPA), and the like.

A high molecular compound such as poly(N-vinylcarbazole) (abbreviation: PVK), poly(4-vinyltriphenylamine) (abbreviation: PVTPA), poly[N-(4-{N′-[4-(4-diphenylamino)phenyl]phenyl-N′-phenylamino}phenyl)methacrylamide] (abbreviation: PTPDMA), or poly[N,N′-bis(4-butylphenyl)-N,N′-bis(phenyl)benzidine] (abbreviation: Poly-TPD) can also be used.

Examples of the substance having an acceptor property which is used for the hole-injection layer 111 and the hole-transport layer 112 are compounds having an electron-withdrawing group (a halogen group or a cyano group) such as 7,7,8,8-tetracyano-2,3,5,6-tetrafluoroquinodimethane (abbreviation: F4-TCNQ), chloranil, and 2,3,6,7,10,11-hexacyano-1,4,5,8,9,12-hexaazatriphenylene (HAT-CN). In particular, a compound in which electron-withdrawing groups are bonded to a condensed aromatic ring having a plurality of hetero atoms, like HAT-CN, is thermally stable and preferable. Oxides of metals belonging to Groups 4 to 8 of the periodic table can be given. Specifically, vanadium oxide, niobium oxide, tantalum oxide, chromium oxide, molybdenum oxide, tungsten oxide, manganese oxide, and rhenium oxide are preferable because of their high electron-accepting properties. Among these, molybdenum oxide is especially preferable since it is stable in the air, has a low hygroscopic property, and is easy to handle.

The light-emitting layer 113 contains a light-emitting substance, which may be a fluorescent substance or a phosphorescent substance. In the light-emitting element of one embodiment of the present invention, the organometallic complex described in Embodiment 1 is preferably used as the light-emitting substance in the light-emitting layer 113. The light-emitting layer 113 preferably contains, as a host material, a substance having higher triplet excitation energy than this organometallic complex (guest material). Alternatively, the light-emitting layer 113 may contain, in addition to the light-emitting substance, two kinds of organic compounds that can form an excited complex (also called an exciplex) at the time of recombination of carriers (electrons and holes) in the light-emitting layer 113 (the two kinds of organic compounds may be any of the host materials described above). In order to form an exciplex efficiently, it is particularly preferable to combine a compound which easily accepts electrons (a material having an electron-transport property) and a compound which easily accepts holes (a material having a hole-transport property). In the case where the combination of a material having an electron-transport property and a material having a hole-transport property which form an exciplex is used as a host material as described above, the carrier balance between holes and electrons in the light-emitting layer can be easily optimized by adjustment of the mixture ratio of the material having an electron-transport property and the material having a hole-transport property. The optimization of the carrier balance between holes and electrons in the light-emitting layer can prevent a region in which electrons and holes are recombined from existing on one side in the light-emitting layer. By preventing the region in which electrons and holes are recombined from existing on one side, the reliability of the light-emitting element can be improved.

As the compound that is preferably used to form the above exciplex and easily accepts electrons (the material having an electron-transport property), a π-electron deficient heteroaromatic compound such as a nitrogen-containing heteroaromatic compound, a metal complex, or the like can be used. Specific examples include metal complexes such as bis(10-hydroxybenzo[h]quinolinato)beryllium(II) (abbreviation: BeBq2), bis(2-methyl-8-quinolinolato)(4-phenylphenolato)aluminum(III) (abbreviation: BAlq), bis(8-quinolinolato)zinc(II) (abbreviation: Znq), bis[2-(2-benzoxazolyl)phenolato]zinc(II) (abbreviation: ZnPBO), and bis[2-(2-benzothiazolyl)phenolato]zinc(II) (abbreviation: ZnBTZ); heterocyclic compounds having polyazole skeletons, such as 2-(4-biphenylyl)-5-(4-tert-butylphenyl)-1,3,4-oxadiazole (abbreviation: PBD), 3-(4-biphenylyl)-4-phenyl-5-(4-tert-butylphenyl)-1,2,4-triazole (abbreviation: TAZ), 1,3-bis[5-(p-tert-butylphenyl)-1,3,4-oxadiazol-2-yl]benzene (abbreviation: OXD-7), 9-[4-(5-phenyl-1,3,4-oxadiazol-2-yl)phenyl]-9H-carbazole (abbreviation: CO11), 2,2′,2″-(1,3,5-benzenetriyl)tris(1-phenyl-1H-benzimidazole) (abbreviation: TPBI), and 2-[3-(dibenzothiophen-4-yl)phenyl]-1-phenyl-1H-benzimidazole (abbreviation: mDBTBIm-II); heterocyclic compounds having diazine skeletons, such as 2-[3-(dibenzothiophen-4-yl)phenyl]dibenzo quinoxaline (abbreviation: 2mDBTPDBq-II), 2-[3′-(dibenzothiophen-4-yl)biphenyl-3-yl]dibenzo[f,h]quinoxaline (abbreviation: 2mDBTBPDBq-II), 2-[3′-(9H-carbazol-9-yl)biphenyl-3-yl]dibenzo[f,h]quinoxaline (abbreviation: 2mCzBPDBq), 2-[4-(3,6-diphenyl-9H-carbazol-9-yl)phenyl]dibenzo[f,h]quinoxaline (abbreviation: 2CzPDBq-III), 7-[3-(dibenzothiophen-4-yl)phenyl]dibenzo[f,h]quinoxaline (abbreviation: 7mDBTPDBq-II), 6-[3-(dibenzothiophen-4-yl)phenyl]dibenzo[f,h]quinoxaline (abbreviation: 6mDBTPDBq-II), 4,6-bis[3-(phenanthren-9-yl)phenyl]pyrimidine (abbreviation: 4,6mPnP2Pm), 4,6-bis[3-(4-dibenzothienyl)phenyl]pyrimidine (abbreviation: 4,6mDBTP2Pm-II), and 4,6-bis[3-(9H-carbazol-9-yl)phenyl]pyrimidine (abbreviation: 4,6mCzP2Pm); heterocyclic compounds having triazine skeletons, such as 2-{4-[3-(N-phenyl-9H-carbazol-3-yl)-9H-carbazol-9-yl]phenyl}-4,6-diphenyl-1,3,5-triazine (abbreviation: PCCzPTzn); and heterocyclic compounds having pyridine skeletons, such as 3,5-bis[3-(9H-carbazol-9-yl)phenyl]pyridine (abbreviation: 35DCzPPy) and 1,3,5-tri[3-(3-pyridyl)phenyl]benzene (abbreviation: TmPyPB). Among the above materials, the heterocyclic compounds having diazine skeletons, those having triazine skeletons, and those having pyridine skeletons are highly reliable and preferred. In particular, the heterocyclic compounds having diazine (pyrimidine or pyrazine) skeletons and those having triazine skeletons have a high electron-transport property and contribute to a decrease in drive voltage.

As the compound that is preferably used to form the above exciplex and easily accepts holes (the material having a hole-transport property), a π-electron rich heteroaromatic compound (e.g., a carbazole derivative or an indole derivative), an aromatic amine compound, or the like can be favorably used. Specific examples include compounds having aromatic amine skeletons, such as 24N-(9-phenylcarbazol-3-yl)-N-phenylaminolspiro-9,9′-bifluorene (abbreviation: PCASF), 4,4′,4″-tris[N-(1-naphthyl)-N-phenylamino]triphenylamine (abbreviation: 1′-TNATA), 2,7-bis[N-(4-diphenylaminophenyl)-N-phenylamino]spiro-9,9′-bifluorene (abbreviation: DPA2SF), -bis(9-phenylcarbazol-3-yl)-N,N′P-diphenylbenzene-1,3-diamine (abbreviation: PCA2B), N-(9,9-dimethyl-2-diphenylamino-9H-fluoren-7-yl)diphenylamine (abbreviation: DPNF), N,N′,N″-triphenyl-N,N′,N″-tris(9-phenylcarbazol-3-yl)benzene-1,3,5-triamine (abbreviation: PCA3B), 2-[N-(4-diphenylaminophenyl)-N-phenylamino]spiro-9,9′-bifluorene (abbreviation: DPASF), N,N′-bis[4-(carbazol-9-yl)phenyl]-N,N′-diphenyl-9,9-dimethylfluorene-2,7-diamine (abbreviation: YGA2F), NPB, N,N′-bis(3-methylphenyl)-N,N′-diphenyl-[1,1′-biphenyl]-4,4′-diamine (abbreviation: TPD), 4,4′-bis[N-(4-diphenylaminophenyl)-N-phenylamino]biphenyl (abbreviation: DPAB), BSPB, 4-phenyl-4′-(9-phenylfluoren-9-yl)triphenylamine (abbreviation: BPAFLP), 4-phenyl-3′-(9-phenylfluoren-9-yl)triphenylamine (abbreviation: mBPAFLP), N-(9,9-dimethyl-9H-fluoren-2-yl)-N-{9,9-dimethyl-2-[N-phenyl-N′-(9,9-dimethyl-9H-fluoren-2-yl)amino]-9H-fluoren-7-yl}phenylamine (abbreviation: DFLADFL), PCzPCA1, 3-[N-(4-diphenylaminophenyl)-N-phenylamino]-9-phenylcarbazole (abbreviation: PCzDPA1), 3,6-bis[N-(4-diphenylaminophenyl)-N-phenylamino]-9-phenylcarbazole (abbreviation: PCzDPA2), DNTPD, 3,6-bis[N-(4-diphenylaminophenyl)-N-(1-naphthyl)amino]-9-phenylcarbazole (abbreviation: PCzTPN2), PCzPCA2, 4-phenyl-4′-(9-phenyl-9H-carbazol-3-yl)triphenylamine (abbreviation: PCBA1BP), 4,4′-diphenyl-4″-(9-phenyl-9H-carbazol-3-yl)triphenylamine (abbreviation: PCBBi1BP), 4-(1-naphthyl)-4′-(9-phenyl-9H-carbazol-3-yl)triphenylamine (abbreviation: PCBANB), 4,4′-di(1-naphthyl)-4″-(9-phenyl-9H-carbazol-3-yl)triphenylamine (abbreviation: PCBNBB), 3-[N-(1-naphthyl)-N-(9-phenylcarbazol-3-yl)amino]-9-phenylcarbazole (abbreviation: PCzPCN1), 9,9-dimethyl-N-phenyl-N-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]fluoren-2-amine (abbreviation: PCBAF), N-phenyl-N-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]spiro-9,9′-bifluoren-2-amine (abbreviation: PCBASF), N-(4-biphenyl)-N-(9,9-dimethyl-9H-fluoren-2-yl)-9-phenyl-9H-carbazol-3-amine (abbreviation: PCBiF), and N-(1,1′-biphenyl-4-yl)-N-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-9,9-dimethyl-9H-fluoren-2-amine (abbreviation: PCBBiF); compounds having carbazole skeletons, such as 1,3-bis(N-carbazolyl)benzene (abbreviation: mCP), CBP, 3,6-bis(3,5-diphenylphenyl)-9-phenylcarbazole (abbreviation: CzTP), and 9-phenyl-9H-3-(9-phenyl-9H-carbazol-3-yl)carbazole (abbreviation: PCCP); compounds having thiophene skeletons, such as 4,4′,4″-(benzene-1,3,5-triyl)tri(dibenzothiophene) (abbreviation: DBT3P-II), 2,8-diphenyl-4-[4-(9-phenyl-9H-fluoren-9-yl)phenyl]dibenzothiophene (abbreviation: DBTFLP-III), and 4-[4-(9-phenyl-9H-fluoren-9-yl)phenyl]-6-phenyldibenzothiophene (abbreviation: DBTFLP-IV); and compounds having furan skeletons, such as 4,4′,4″-(benzene-1,3,5-triyl)tri(dibenzofuran) (abbreviation: DBF3P-II) and 4-{3-[3-(9-phenyl-9H-fluoren-9-yl)phenyl]phenyl}dibenzofuran (abbreviation: mmDBFFLBi-II). Among the above materials, the compounds having aromatic amine skeletons and the compounds having carbazole skeletons are preferred because these compounds are highly reliable, have a high hole-transport property, and contribute to a reduction in drive voltage.

Note that in the case where the light-emitting layer 113 contains the above-described organometallic complex (guest material) and the host material, phosphorescence with high emission efficiency can be obtained from the light-emitting layer 113.

In the light-emitting element, the light-emitting layer 113 does not necessarily have the single-layer structure shown in FIG. 1A and may have a stacked-layer structure including two or more layers as shown in FIG. 1B. In that case, each layer in the stacked-layer structure emits light. For example, fluorescence is obtained from a first light-emitting layer 113(a 1), and phosphorescence is obtained from a second light-emitting layer 113(a 2) stacked over the first light-emitting layer 113(a 1). Note that the stacking order may be reversed. It is preferable that light emission due to energy transfer from an exciplex to a dopant be obtained from the layer that emits phosphorescence. The emission color of one layer and that of the other layer may be the same or different. In the case where the emission colors are different, a structure in which, for example, blue light from one layer and orange or yellow light or the like from the other layer can be obtained can be formed. Each layer may contain a plurality of kinds of dopants.

Note that in the case where the light-emitting layer 113 has a stacked-layer structure, for example, the organometallic complex described in Embodiment 1, a light-emitting substance converting singlet excitation energy into light emission, and a light-emitting substance converting triplet excitation energy into light emission can be used alone or in combination. In that case, the following substances can be used, for example.

As an example of the light-emitting substance converting singlet excitation energy into light emission, a substance which emits fluorescence (a fluorescent compound) can be given.

Examples of the substance which emits fluorescence are N,N′-bis[4-(9H-carbazol-9-yl)phenyl]-N,N′-diphenylstilbene-4,4′-diamine (abbreviation: YGA2S), 4-(9H-carbazol-9-yl)-4′-(10-phenyl-9-anthryl)triphenylamine (abbreviation: YGAPA), 4-(9H-carbazol-9-yl)-4′-(9,10-diphenyl-2-anthryl)triphenylamine (abbreviation: 2YGAPPA), N,9-diphenyl-N-[4-(10-phenyl-9-anthryl)phenyl]-9H-carbazol-3-amine (abbreviation: PCAPA), perylene, 2,5,8,11-tetra(tert-butyl)perylene (abbreviation: TBP), 4-(10-phenyl-9-anthryl)-4′-(9-phenyl-9H-carbazol-3-yl)triphenylamine (abbreviation: PCBAPA), N,N″-(2-tert-butylanthracene-9,10-diyldi-4,1-phenylene)bis[N,N′,N″-triphenyl-1,4-phenylenediamine] (abbreviation: DPABPA), N,9-diphenyl-N-[4-(9,10-diphenyl-2-anthryl)phenyl]-9H-carbazol-3-amine (abbreviation: 2PCAPPA), N-[4-(9,10-diphenyl-2-anthryl)phenyl]-N,N′,N′-triphenyl-1,4-phenylenediamine (abbreviation: 2DPAPPA), N,N,N′,N′,N″,N″,N′″,N′″-octaphenyldibenzo[g,p]chrysene-2,7,10,15-tetraamine (abbreviation: DBC1), coumarin 30, N-(9,10-diphenyl-2-anthryl)-N,9-diphenyl-9H-carbazol-3-amine (abbreviation: 2PCAPA), N-[9,10-bis(1,1′-biphenyl-2-yl)-2-anthryl]-N,9-diphenyl-9H-carbazol-3-amine (abbreviation: 2PCABPhA), N-(9,10-diphenyl-2-anthryl)-N,N′,N′-triphenyl-1,4-phenylenedi amine (abbreviation: 2DPAPA), N-[9,10-bis(1,1′-biphenyl-2-yl)-2-anthryl]-N,N′,N′-triphenyl-1,4-phenylenediamine (abbreviation: 2DPABPhA), 9,10-bis(1,1′-biphenyl-2-yl)-N-[4-(9H-carbazol-9-yl)phenyl]-N-phenylanthracen-2-amine (abbreviation: 2YGABPhA), N,N,9-triphenylanthracen-9-amine (abbreviation: DPhAPhA), coumarin 545T, N,N′-diphenylquinacridone (abbreviation: DPQd), rubrene, 5,12-bis(1,1′-biphenyl-4-yl)-6,11-diphenyltetracene (abbreviation: BPT), 2-(2-{2-[4-(dimethylamino)phenyl]ethenyl}-6-methyl-4H-pyran-4-ylidene)propanedinitrile (abbreviation: DCM1), 2-{2-methyl-6-[2-(2,3,6,7-tetrahydro-1H,5H-benzo[ij]quinolizin-9-yl)ethenyl]-4H-pyran-4-ylidene}propanedinitrile (abbreviation: DCM2), N,N,N′,N′-tetrakis(4-methylphenyl)tetracene-5,11-diamine (abbreviation: p-mPhTD), 7,14-diphenyl-N,N,N′,N′-tetrakis(4-methylphenyl)acenaphtho[1,2-a]fluoranthene-3,10-diamine (abbreviation: p-mPhAFD), {2-isopropyl-6-[2-(1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H,5H-benzo[ij]quinolizin-9-yl)ethenyl]-4H-pyran-4-ylidene}propanedinitrile (abbreviation: DCJTI), {2-tert-butyl-6-[2-(1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H,5H-benzo[ij]quinolizin-9-yl)ethenyl]-4H-pyran-4-ylidene}propanedinitrile (abbreviation: DCJTB), 2-(2,6-bis{2-[4-(dimethylamino)phenyl]ethenyl}-4H-pyran-4-ylidene)propanedinitrile (abbreviation: BisDCM), 2-{2,6-bis[2-(8-methoxy-1,1,7,7-tetramethyl-2,3,6,7-tetrahydro-1H,5H-benzo[ij]quinolizin-9-yl)ethenyl]-4H-pyran-4-ylidene}propanedinitrile (abbreviation: BisDCJTM), and the like.

Examples of the light-emitting substance converting triplet excitation energy into light emission are a substance which emits phosphorescence (a phosphorescent compound) and a thermally activated delayed fluorescent (TADF) material which emits thermally activated delayed fluorescence. Note that “delayed fluorescence” exhibited by the TADF material refers to light emission having the same spectrum as normal fluorescence and an extremely long lifetime. The lifetime is 1×10⁻⁶ seconds or longer, preferably 1×10⁻³ seconds or longer.

Examples of the substance which emits phosphorescence are bis{2-[3′,5′-bis(trifluoromethyl)phenyl]pyridinato-N,C^(2′)}iridium (III) picolinate (abbreviation: [Ir(CF₃ppy)₂(pic)]), bis[2-(4′,6′-difluorophenyl)pyridinato-N,C^(2′)]iridium(III) acetylacetonate (abbreviation: FIr(acac)), tris(2-phenylpyridinato)iridium(III) (abbreviation: [Ir(ppy)₃]), bis(2-phenylpyridinato)iridium(III) acetylacetonate (abbreviation: [Ir(ppy)₂(acac)]), tris(acetylacetonato)(monophenanthroline)terbium(III) (abbreviation: [Tb(acac)₃(Phen)]), bis(benzo[h]quinolinato)iridium(III) acetylacetonate (abbreviation: [Ir(bzq)₂(acac)]), bis(2,4-diphenyl-1,3-oxazolato-N,C^(2′))iridium(III) acetylacetonate (abbreviation: [Ir(dpo)₂(acac)]), bis{2-[4′-(perfluorophenyl)phenyl]pyridinato-N,C^(2′)}iridium(III) acetylacetonate (abbreviation: [Ir(p-PF-ph)₂(acac)]), bis(2-phenylbenzothiazolato-N,C^(2′))iridium(III) acetylacetonate (abbreviation: [Ir(bt)₂(acac)]), bis[2-(2′-benzo[4,5-a]thienyl)pyridinato-N,C^(3′)]iridium(III) acetylacetonate (abbreviation: [Ir(btp)₂(acac)]), bis(1-phenylisoquinolinato-N,C^(2′))iridium(III) acetylacetonate (abbreviation: [Ir(piq)₂(acac)]), (acetylacetonato)bis[2,3-bis(4-fluorophenyl)quinoxalinato]iridium(III) (abbreviation: [Ir(Fdpq)₂(acac)]), (acetylacetonato)bis(3,5-dimethyl-2-phenylpyrazinato)iridium(III) (abbreviation: [Ir(mppr-Me)₂(acac)]), (acetylacetonato)bis(5-isopropyl-3-methyl-2-phenylpyrazinato)iridium(III) (abbreviation: [Ir(mppr-iPr)₂(acac)]), (acetylacetonato)bis(2,3,5-triphenylpyrazinato)iridium(III) (abbreviation: [Ir(tppr)₂(acac)]), bis(2,3,5-triphenylpyrazinato)(dipivaloylmethanato)iridium(III) (abbreviation: [Ir(tppr)₂(dpm)]), (acetylacetonato)bis(6-tert-butyl-4-phenylpyrimidinato)iridium(III) (abbreviation: [Ir(tBuppm)₂(acac)]), (acetylacetonato)bis(4,6-diphenylpyrimidinato)iridium(III) (abbreviation: [Ir(dppm)₂(acac)]), 2,3,7,8,12,13,17,18-octaethyl-21H,23H-porphyrin platinum(II) (abbreviation: PtOEP), tris(1,3-diphenyl-1,3-propanedionato)(monophenanthroline)europium(III) (abbreviation: [Eu(DBM)₃(Phen)]), tris[1-(2-thenoyl)-3,3,3-trifluoroacetonato](monophenanthroline)europium(III) (abbreviation: [Eu(TTA)₃(Phen)]), and the like.

Examples of the TADF material are fullerene, a derivative thereof, an acridine derivative such as proflavine, eosin, and the like. Another example is a metal-containing porphyrin, such as a porphyrin containing magnesium (Mg), zinc (Zn), cadmium (Cd), tin (Sn), platinum (Pt), indium (In), or palladium (Pd). Examples of the metal-containing porphyrin are a protoporphyrin-tin fluoride complex (abbreviation: SnF₂(Proto IX)), a mesoporphyrin-tin fluoride complex (abbreviation: SnF₂(Meso IX)), a hematoporphyrin-tin fluoride complex (abbreviation: SnF₂(Hemato IX)), a coproporphyrin tetramethyl ester-tin fluoride complex (abbreviation: SnF₂(Copro III-4Me)), an octaethylporphyrin-tin fluoride complex (abbreviation: SnF₂(OEP)), an etioporphyrin-tin fluoride complex (abbreviation: SnF₂(Etio I)), an octaethylporphyrin-platinum chloride complex (abbreviation: PtCl₂OEP), and the like. Alternatively, a heterocyclic compound including a π-electron rich heteroaromatic ring and a π-electron deficient heteroaromatic ring can be used, such as 2-(biphenyl-4-yl)-4,6-bis(12-phenylindolo[2,3-a]carbazol-11-yl)-1,3,5-triazine (abbreviation: PIC-TRZ). Note that a substance in which the π-electron rich heteroaromatic ring is directly bonded to the π-electron deficient heteroaromatic ring is particularly preferable because both the donor property of the π-electron rich heteroaromatic ring and the acceptor property of the π-electron deficient heteroaromatic ring are increased and the energy difference between the S1 level and the T1 level becomes small.

The light-emitting layer 113 can be formed using a quantum dot (QD) having unique optical characteristics. Note that QD means a nanoscale semiconductor crystal. Specifically, the nanoscale semiconductor crystal has a diameter of several nanometers to several tens of nanometers. Furthermore, by using a crystal having a different size, the optical characteristics and the electronic characteristics can be changed, and thus an emission color or the like can be adjusted easily. A quantum dot has an emission spectrum with a narrow peak, and thus emission of light with high color purity can be obtained.

Examples of a material forming a quantum dot include a Group 14 element of the periodic table, a Group 15 element of the periodic table, a Group 16 element of the periodic table, a compound of a plurality of Group 14 elements of the periodic table, a compound of an element belonging to any of Groups 4 to 14 of the periodic table and a Group 16 element of the periodic table, a compound of a Group 2 element of the periodic table and a Group 16 element of the periodic table, a compound of a Group 13 element of the periodic table and a Group 15 element of the periodic table, a compound of a Group 13 element of the periodic table and a Group 17 element of the periodic table, a compound of a Group 14 element of the periodic table and a Group 15 element of the periodic table, a compound of a Group 11 element of the periodic table and a Group 17 element of the periodic table, iron oxides, titanium oxides, spinel chalcogenides, semiconductor clusters, and the like.

Specific examples include, but are not limited to, cadmium selenide; cadmium sulfide; cadmium telluride; zinc selenide; zinc oxide; zinc sulfide; zinc telluride; mercury sulfide; mercury selenide; mercury telluride; indium arsenide; indium phosphide; gallium arsenide; gallium phosphide; indium nitride; gallium nitride; indium antimonide; gallium antimonide; aluminum phosphide; aluminum arsenide; aluminum antimonide; lead selenide; lead telluride; lead sulfide; indium selenide; indium telluride; indium sulfide; gallium selenide; arsenic sulfide; arsenic selenide; arsenic telluride; antimony sulfide; antimony selenide; antimony telluride; bismuth sulfide; bismuth selenide; bismuth telluride; silicon; silicon carbide; germanium; tin; selenium; tellurium; boron; carbon; phosphorus; boron nitride; boron phosphide; boron arsenide; aluminum nitride; aluminum sulfide; barium sulfide; barium selenide; barium telluride; calcium sulfide; calcium selenide; calcium telluride; beryllium sulfide; beryllium selenide; beryllium telluride; magnesium sulfide; magnesium selenide; germanium sulfide; germanium selenide; germanium telluride; tin sulfide; tin selenide; tin telluride; lead oxide; copper fluoride; copper chloride; copper bromide; copper iodide; copper oxide; copper selenide; nickel oxide; cobalt oxide; cobalt sulfide; iron oxide; iron sulfide; manganese oxide; molybdenum sulfide; vanadium oxide; tungsten oxide; tantalum oxide; titanium oxide; zirconium oxide; silicon nitride; germanium nitride; aluminum oxide; barium titanate; a compound of selenium, zinc, and cadmium; a compound of indium, arsenic, and phosphorus; a compound of cadmium, selenium, and sulfur; a compound of cadmium, selenium, and tellurium; a compound of indium, gallium, and arsenic; a compound of indium, gallium, and selenium; a compound of indium, selenium, and sulfur; a compound of copper, indium, and sulfur; combinations thereof; and the like. What is called an alloyed quantum dot, whose composition is represented by a given ratio, may be used. For example, an alloyed quantum dot of cadmium, selenium, and sulfur is an effective material to obtain blue light because the emission wavelength can be changed by changing the percentages of the elements.

As a structure of a quantum dot, a core structure, a core-shell structure, a core-multishell structure, or the like can be given, and any of the structures may be used. Note that a core-shell quantum dot or a core-multishell quantum dot where a shell covers a core is preferable because a shell formed of an inorganic material having a wider band gap than an inorganic material used as the core can reduce the influence of defects and dangling bonds existing at the surface of the nanocrystal and significantly improve the quantum efficiency of light emission.

Moreover, QD can be dispersed into a solution, and thus the light-emitting layer 113 can be formed by a coating method, an ink-jet method, a printing method, or the like. Note that QD can emit not only light with bright and vivid color but also light with a wide range of wavelengths and has high efficiency and long lifetime. Thus, when QD is included in the light-emitting layer 113, the element characteristics can be improved.

The electron-transport layer 114 is a layer containing a substance having a high electron-transport property (also referred to as an electron-transport compound). For the electron-transport layer 114, a metal complex such as tris(8-quinolinolato)aluminum (abbreviation: Alq₃), tris(4-methyl-8-quinolinolato)aluminum (abbreviation: Almq₃), BeBq₂, BAlq, bis[2-(2-hydroxyphenyl)benzoxazolato]zinc (abbreviation: Zn(BOX)₂), or bis[2-(2-hydroxyphenyl)benzothiazolato]zinc (abbreviation: Zn(BTZ)₂) can be used. Alternatively, a heteroaromatic compound such as PBD, 1,3-bis[5-(p-tert-butylphenyl)-1,3,4-oxadiazol-2-yl]benzene (abbreviation: OXD-7), TAZ, 3-(4-tert-butylphenyl)-4-(4-ethylphenyl)-5-(4-biphenylyl)-1,2,4-triazole (abbreviation: p-EtTAZ), bathophenanthroline (abbreviation: BPhen), bathocuproine (abbreviation: BCP), or 4,4′-bis(5-methylbenzoxazol-2-yl)stilbene (abbreviation: BzOs) can also be used. A high molecular compound such as poly(2,5-pyridinediyl) (abbreviation: PPy), poly[(9,9-dihexylfluorene-2,7-diyl)-co-(pyridine-3,5-diyl)] (abbreviation: PF-Py), or poly[(9,9-dioctylfluorene-2,7-diyl)-co-(2,2′-bipyridine-6,6′-diyl)] (abbreviation: PF-BPy) can also be used. The substances listed here are mainly ones that have an electron mobility of 1×10⁻⁶ cm²/Vs or higher. Note that any substance other than the substances listed here may be used for the electron-transport layer 114 as long as the electron-transport property is higher than the hole-transport property.

The electron-transport layer 114 is not limited to a single layer, and may be a stack including two or more layers each containing any of the substances listed above.

The electron-injection layer 115 is a layer containing a substance having a high electron-injection property. For the electron-injection layer 115, an alkali metal, an alkaline earth metal, or a compound thereof, such as lithium fluoride (LiF), cesium fluoride (CsF), calcium fluoride (CaF₂), or lithium oxide (LiO_(x)) can be used. A rare earth metal compound such as erbium fluoride (ErF₃) can also be used. An electride may also be used for the electron-injection layer 115. Examples of the electride include a substance in which electrons are added at high concentration to calcium oxide-aluminum oxide and the like. Any of the substances for forming the electron-transport layer 114, which are given above, can be used.

A composite material in which an organic compound and an electron donor (donor) are mixed may also be used for the electron-injection layer 115. Such a composite material is excellent in an electron-injection property and an electron-transport property because electrons are generated in the organic compound by the electron donor. In this case, the organic compound is preferably a material that is excellent in transporting the generated electrons. Specifically, for example, the substances for forming the electron-transport layer 114 (e.g., a metal complex or a heteroaromatic compound), which are given above, can be used. As the electron donor, a substance showing an electron-donating property with respect to the organic compound may be used. Specifically, an alkali metal, an alkaline earth metal, and a rare earth metal are preferable, and lithium, cesium, magnesium, calcium, erbium, ytterbium, and the like are given. In addition, an alkali metal oxide or an alkaline earth metal oxide is preferable, and lithium oxide, calcium oxide, barium oxide, and the like are given. A Lewis base such as magnesium oxide can also be used. An organic compound such as tetrathiafulvalene (abbreviation: TTF) can also be used.

Note that each of the hole-injection layer 111, the hole-transport layer 112, the light-emitting layer 113, the electron-transport layer 114, and the electron-injection layer 115 can be formed by any one or any combination of the following methods: an evaporation method (including a vacuum evaporation method), a printing method (such as relief printing, intaglio printing, gravure printing, planography printing, and stencil printing), an ink-jet method, a coating method, and the like. Besides the above-mentioned materials, an inorganic compound such as a quantum dot or a high molecular compound (e.g., an oligomer, a dendrimer, or a polymer) may be used for the hole-injection layer 111, the hole-transport layer 112, the light-emitting layer 113, the electron-transport layer 114, and the electron-injection layer 115, which are described above.

In the above-described light-emitting element, current flows because of a potential difference applied between the first electrode 101 and the second electrode 103 and holes and electrons recombine in the EL layer 102, whereby light is emitted. Then, the light emission is extracted to the outside through one or both of the first electrode 101 and the second electrode 103. Thus, one or both of the first electrode 101 and the second electrode 103 are electrodes having light-transmitting properties.

The above-described light-emitting element can emit phosphorescence originating from the organometallic complex and thus can have higher efficiency than a light-emitting element using only a fluorescent compound.

Note that the structures described in this embodiment can be combined with any of the structures described in the other embodiments as appropriate.

Embodiment 3

In this embodiment, a light-emitting element (hereinafter referred to as a tandem light-emitting element) which is one embodiment of the present invention and includes a plurality of EL layers is described.

A light-emitting element described in this embodiment is a tandem light-emitting element including, between a pair of electrodes (a first electrode 201 and a second electrode 204), a plurality of EL layers (a first EL layer 202(1) and a second EL layer 202(2)) and a charge-generation layer 205 provided therebetween, as illustrated in FIG. 2A.

In this embodiment, the first electrode 201 functions as an anode, and the second electrode 204 functions as a cathode. Note that the first electrode 201 and the second electrode 204 can have structures similar to those described in Embodiment 2. In addition, either or both of the EL layers (the first EL layer 202(1) and the second EL layer 202(2)) may have structures similar to those described in Embodiment 2. In other words, the structures of the first EL layer 202(1) and the second EL layer 202(2) may be the same or different from each other. When the structures are the same, Embodiment 2 can be referred to.

The charge-generation layer 205 provided between the plurality of EL layers (the first EL layer 202(1) and the second EL layer 202(2)) has a function of injecting electrons into one of the EL layers and injecting holes into the other of the EL layers when a voltage is applied between the first electrode 201 and the second electrode 204. In this embodiment, when a voltage is applied such that the potential of the first electrode 201 is higher than that of the second electrode 204, the charge-generation layer 205 injects electrons into the first EL layer 202(1) and injects holes into the second EL layer 202(2).

Note that in terms of light extraction efficiency, the charge-generation layer 205 preferably has a property of transmitting visible light (specifically, the charge-generation layer 205 has a visible light transmittance of 40% or more). The charge-generation layer 205 functions even when it has lower conductivity than the first electrode 201 or the second electrode 204.

The charge-generation layer 205 may have either a structure in which an electron acceptor (acceptor) is added to an organic compound having a high hole-transport property or a structure in which an electron donor (donor) is added to an organic compound having a high electron-transport property. Alternatively, both of these structures may be stacked.

In the case of the structure in which an electron acceptor is added to an organic compound having a high hole-transport property, as the organic compound having a high hole-transport property, the substances having a high hole-transport property which are given in Embodiment 2 and used for the hole-injection layer 111 and the hole-transport layer 112 can be used. For example, an aromatic amine compound such as NPB, TPD, TDATA, MTDATA, or BSPB, or the like can be used. The substances listed here are mainly ones that have a hole mobility of 1×10⁻⁶ cm²/Vs or higher. Note that any organic compound other than the compounds listed here may be used as long as the hole-transport property is higher than the electron-transport property.

As the electron acceptor, 7,7,8,8-tetracyano-2,3,5,6-tetrafluoroquinodimethane (abbreviation: F₄-TCNQ), chloranil, and the like can be given. Oxides of metals belonging to Groups 4 to 8 of the periodic table can also be given. Specifically, vanadium oxide, niobium oxide, tantalum oxide, chromium oxide, molybdenum oxide, tungsten oxide, manganese oxide, and rhenium oxide are preferable because of their high electron-accepting properties. Among these, molybdenum oxide is especially preferable since it is stable in the air, has a low hygroscopic property, and is easy to handle.

In the case of the structure in which an electron donor is added to an organic compound having a high electron-transport property, as the organic compound having a high electron-transport property, the substances having a high electron-transport property which are given in Embodiment 2 and used for the electron-transport layer 114 can be used. For example, a metal complex having a quinoline skeleton or a benzoquinoline skeleton, such as Alq, Almq₃, BeBq₂, or BAlq, or the like can be used. Alternatively, a metal complex having an oxazole-based ligand or a thiazole-based ligand, such as Zn(BOX)₂ or Zn(BTZ)₂, can be used. Alternatively, in addition to such a metal complex, PBD, OXD-7, TAZ, BPhen, BCP, or the like can be used. The substances listed here are mainly ones that have an electron mobility of 1×10⁻⁶ cm²/Vs or higher. Note that any organic compound other than the compounds listed here may be used as long as the electron-transport property is higher than the hole-transport property.

As the electron donor, it is possible to use an alkali metal, an alkaline earth metal, a rare earth metal, metals belonging to Groups 2 and 13 of the periodic table, or an oxide or carbonate thereof. Specifically, lithium (Li), cesium (Cs), magnesium (Mg), calcium (Ca), ytterbium (Yb), indium (In), lithium oxide, cesium carbonate, or the like is preferably used. Alternatively, an organic compound such as tetrathianaphthacene may be used as the electron donor.

Note that forming the charge-generation layer 205 by using any of the above materials can suppress a drive voltage increase caused by the stack of the EL layers. The charge-generation layer 205 can be formed by any one or any combination of the following methods: an evaporation method (including a vacuum evaporation method), a printing method (such as relief printing, intaglio printing, gravure printing, planography printing, and stencil printing), an ink-jet method, a coating method, and the like.

Although the light-emitting element including two EL layers is described in this embodiment, the present invention can be similarly applied to a light-emitting element in which n EL layers (202(1) to 202(n)) (n is three or more) are stacked as illustrated in FIG. 2B. In the case where a plurality of EL layers are included between a pair of electrodes as in the light-emitting element according to this embodiment, by providing charge-generation layers (205(1) to 205(n−1)) between the EL layers, light emission in a high luminance region can be obtained with current density kept low. Since the current density can be kept low, the element can have long lifetime.

When the EL layers have different emission colors, a desired emission color can be obtained from the whole light-emitting element. For example, in a light-emitting element having two EL layers, when an emission color of the first EL layer and an emission color of the second EL layer are complementary colors, the light-emitting element can emit white light as a whole. Note that “complementary colors” refer to colors that can produce an achromatic color when mixed. In other words, mixing light of complementary colors allows white emission to be obtained. Specifically, a combination in which blue light emission is obtained from the first EL layer and yellow or orange light emission is obtained from the second EL layer is given as an example. In that case, it is not necessary that blue light emission and yellow (or orange) light emission are both fluorescence or both phosphorescence. For example, a combination in which blue light emission is fluorescence and yellow (or orange) light emission is phosphorescence or a combination in which blue light emission is phosphorescence and yellow (or orange) light emission is fluorescence may be employed.

The same applies to a light-emitting element having three EL layers. For example, the light-emitting element as a whole can provide white light emission when the emission color of the first EL layer is red, the emission color of the second EL layer is green, and the emission color of the third EL layer is blue.

Note that the structures described in this embodiment can be combined with any of the structures described in the other embodiments as appropriate.

Embodiment 4

In this embodiment, a light-emitting device of one embodiment of the present invention is described.

The light-emitting device may be either a passive matrix light-emitting device or an active matrix light-emitting device. Any of the light-emitting elements described in the other embodiments can be used for the light-emitting device described in this embodiment.

In this embodiment, first, an active matrix light-emitting device is described with reference to FIGS. 3A to 3C.

Note that FIG. 3A is a top view illustrating a light-emitting device, and FIG. 3B is a cross-sectional view taken along chain line A-A′ in FIG. 3A. The light-emitting device according to this embodiment includes a pixel portion 302 provided over an element substrate 301, a driver circuit portion (a source line driver circuit) 303, and driver circuit portions (gate line driver circuits) 304 a and 304 b. The pixel portion 302, the driver circuit portion 303, and the driver circuit portions 304 a and 304 b are sealed between the element substrate 301 and a sealing substrate 306 with a sealant 305.

In addition, over the element substrate 301, a lead wiring 307 for connecting an external input terminal, through which a signal (e.g., a video signal, a clock signal, a start signal, or a reset signal) or a potential from the outside is transmitted to the driver circuit portion 303 and the driver circuit portions 304 a and 304 b, is provided. Here, an example is described in which a flexible printed circuit (FPC) 308 is provided as the external input terminal. Although only the FPC is illustrated here, the FPC may be provided with a printed wiring board (PWB). The light-emitting device in this specification includes, in its category, not only the light-emitting device itself but also the light-emitting device provided with the FPC or the PWB.

Next, a cross-sectional structure is described with reference to FIG. 3B. The driver circuit portions and the pixel portion are formed over the element substrate 301; the driver circuit portion 303 that is the source line driver circuit and the pixel portion 302 are illustrated here.

The driver circuit portion 303 is an example in which an FET 309 and an FET 310 are combined. Note that the driver circuit portion 303 may be formed with a circuit including transistors having the same conductivity type (either n-channel transistors or p-channel transistors) or a CMOS circuit including an n-channel transistor and a p-channel transistor. Although this embodiment shows a driver integrated type in which the driver circuit is formed over the substrate, the driver circuit is not necessarily formed over the substrate, and may be formed outside the substrate.

The pixel portion 302 includes switching FETs (not shown) and current control FETs 312, and wirings of the current control FETs 312 (source electrodes or drain electrodes) are electrically connected to first electrodes (anodes) (313 a and 313 b) of light-emitting elements 317 a and 317 b. Although the pixel portion 302 includes two kinds of FETs (the switching FETs and the current control FETs 312) in this embodiment, one embodiment of the present invention is not limited thereto. The pixel portion 302 may include, for example, three or more kinds of FETs and capacitors in combination.

As the FETs 309, 310, and 312, for example, a staggered transistor or an inverted staggered transistor can be used. Examples of a semiconductor material that can be used for the FETs 309, 310, and 312 include Group 13 semiconductors, Group 14 semiconductors (e.g., silicon), compound semiconductors, oxide semiconductors, and organic semiconductors. In addition, there is no particular limitation on the crystallinity of the semiconductor material, and an amorphous semiconductor or a crystalline semiconductor can be used. In particular, an oxide semiconductor is preferably used for the FETs 309, 310, and 312. Examples of the oxide semiconductor are In—Ga oxides, In-M-Zn oxides (M is Al, Ga, Y, Zr, La, Ce, Hf, or Nd), and the like. For example, an oxide semiconductor that has an energy gap of 2 eV or more, preferably 2.5 eV or more, further preferably 3 eV or more is used for the FETs 309, 310, and 312, so that the off-state current of the transistors can be reduced.

In addition, conductive films (320 a and 320 b) for optical adjustment are stacked over the first electrodes (313 a and 313 b). For example, as illustrated in FIG. 3B, in the case where the wavelengths of light extracted from the light-emitting elements 317 a and 317 b are different from each other, the thicknesses of the conductive films 320 a and 320 b are different from each other. In addition, an insulator 314 is formed to cover end portions of the first electrodes (313 a and 313 b). In this embodiment, the insulator 314 is formed using a positive photosensitive acrylic resin. The first electrodes (313 a and 313 b) are used as anodes in this embodiment.

The insulator 314 preferably has a surface with curvature at an upper end portion or a lower end portion thereof. This enables the coverage with a film to be formed over the insulator 314 to be favorable. The insulator 314 can be formed using, for example, either a negative photosensitive resin or a positive photosensitive resin. The material for the insulator 314 is not limited to an organic compound and an inorganic compound such as silicon oxide, silicon oxynitride, or silicon nitride can also be used.

An EL layer 315 and a second electrode 316 are stacked over the first electrodes (313 a and 313 b). In the EL layer 315, at least a light-emitting layer is provided. In the light-emitting elements (317 a and 317 b) including the first electrodes (313 a and 313 b), the EL layer 315, and the second electrode 316, an end portion of the EL layer 315 is covered with the second electrode 316. The structure of the EL layer 315 may be the same as or different from the single-layer structure and the stacked-layer structure described in Embodiments 2 and 3. Furthermore, the structure may differ between the light-emitting elements.

For the first electrodes (313 a and 313 b), the EL layer 315, and the second electrode 316, any of the materials given in Embodiment 2 can be used. The first electrodes (313 a and 313 b) of the light-emitting elements (317 a and 317 b) are electrically connected to the lead wiring 307 in a region 321, so that an external signal is input through the FPC 308. The second electrode 316 of the light-emitting elements (317 a and 317 b) is electrically connected to a lead wiring 323 in a region 322, so that an external signal is input through the FPC 308 that is not illustrated in the figure.

Although the cross-sectional view in FIG. 3B illustrates only the two light-emitting elements (317 a and 317 b), a plurality of light-emitting elements are arranged in a matrix in the pixel portion 302. Specifically, in the pixel portion 302, light-emitting elements that emit light of two kinds of colors (e.g., B and Y), light-emitting elements that emit light of three kinds of colors (e.g., R, G, and B), light-emitting elements that emit light of four kinds of colors (e.g., (R, G, B, and Y) or (R, G, B, and W)), or the like are formed so that a light-emitting device capable of full color display can be obtained. In such cases, full color display may be achieved as follows: materials different according to the emission colors or the like of the light-emitting elements are used to form light-emitting layers (so-called separate coloring formation); alternatively, the plurality of light-emitting elements share one light-emitting layer formed using the same material and further include color filters. Thus, the light-emitting elements that emit light of a plurality of kinds of colors are used in combination, so that effects such as an improvement in color purity and a reduction in power consumption can be achieved. Furthermore, the light-emitting device may have improved emission efficiency and reduced power consumption by combination with quantum dots.

The sealing substrate 306 is attached to the element substrate 301 with the sealant 305, whereby the light-emitting elements 317 a and 317 b are provided in a space 318 surrounded by the element substrate 301, the sealing substrate 306, and the sealant 305.

The sealing substrate 306 is provided with coloring layers (color filters) 324, and a black layer (black matrix) 325 is provided between adjacent coloring layers. Note that one or both of the adjacent coloring layers (color filters) 324 may be provided so as to partly overlap with the black layer (black matrix) 325. Light emission obtained from the light-emitting elements 317 a and 317 b is extracted through the coloring layers (color filters) 324.

Note that the space 318 may be filled with an inert gas (such as nitrogen or argon) or the sealant 305. In the case where the sealant is applied for attachment of the substrates, one or more of UV treatment, heat treatment, and the like are preferably performed.

An epoxy-based resin or glass frit is preferably used for the sealant 305. It is preferable that such a material not be permeable to moisture or oxygen as much as possible. As the sealing substrate 306, a glass substrate, a quartz substrate, or a plastic substrate formed of fiber-reinforced plastic (FRP), polyvinyl fluoride (PVF), polyester, an acrylic resin, or the like can be used. In the case where glass frit is used as the sealant, the element substrate 301 and the sealing substrate 306 are preferably glass substrates for high adhesion.

Structures of the FETs electrically connected to the light-emitting elements may be different from those in FIG. 3B in the position of a gate electrode; that is, the structures may be the same as those of an FET 326, an FET 327, and an FET 328, as illustrated in FIG. 3C. The coloring layer (color filter) 324 with which the sealing substrate 306 is provided may be provided as illustrated in FIG. 3C such that, at a position where the coloring layer (color filter) 324 overlaps with the black layer (black matrix) 325, the coloring layer (color filter) 324 further overlaps with an adjacent coloring layer (color filter) 324.

As described above, the active matrix light-emitting device can be obtained.

The light-emitting device of one embodiment of the present invention may be of the passive matrix type, instead of the active matrix type described above.

FIGS. 4A and 4B illustrate a passive matrix light-emitting device. FIG. 4A is a top view of the passive matrix light-emitting device, and FIG. 4B is a cross-sectional view thereof.

As illustrated in FIGS. 4A and 4B, light-emitting elements 405 including a first electrode 402, EL layers (403 a, 403 b, and 403 c), and second electrodes 404 are formed over a substrate 401. Note that the first electrode 402 has an island-like shape, and a plurality of the first electrodes 402 are formed in one direction (the lateral direction in FIG. 4A) to form a striped pattern. An insulating film 406 is formed over part of the first electrode 402. A partition 407 formed using an insulating material is provided over the insulating film 406. The sidewalls of the partition 407 slope so that the distance between one sidewall and the other sidewall gradually decreases toward the surface of the substrate as illustrated in FIG. 4B.

Since the insulating film 406 includes openings over the part of the first electrode 402, the EL layers (403 a, 403 b, and 403 c) and the second electrodes 404 which are divided as desired can be formed over the first electrode 402. In the example in FIGS. 4A and 4B, a mask such as a metal mask and the partition 407 over the insulating film 406 are employed to form the EL layers (403 a, 403 b, and 403 c) and the second electrodes 404. In this example, the EL layer 403 a, the EL layer 403 b, and the EL layer 403 c emit light of different colors (e.g., red, green, blue, yellow, orange, and white).

After the formation of the EL layers (403 a, 403 b, and 403 c), the second electrodes 404 are formed. Thus, the second electrodes 404 are formed over the EL layers (403 a, 403 b, and 403 c) without contact with the first electrode 402.

Note that sealing can be performed by a method similar to that used for the active matrix light-emitting device, and description thereof is not made.

As described above, the passive matrix light-emitting device can be obtained.

In this specification and the like, a transistor or a light-emitting element can be formed using any of a variety of substrates, for example. The type of a substrate is not limited to a certain type. As the substrate, a semiconductor substrate (e.g., a single crystal substrate or a silicon substrate), an SOI substrate, a glass substrate, a quartz substrate, a plastic substrate, a metal substrate, a stainless steel substrate, a substrate including stainless steel foil, a tungsten substrate, a substrate including tungsten foil, a flexible substrate, an attachment film, paper including a fibrous material, a base material film, or the like can be used, for example. As examples of the glass substrate, a barium borosilicate glass substrate, an aluminoborosilicate glass substrate, a soda lime glass substrate, and the like can be given. Examples of the flexible substrate, the attachment film, the base material film, and the like are substrates of plastics typified by polyethylene terephthalate (PET), polyethylene naphthalate (PEN), polyether sulfone (PES), and polytetrafluoroethylene (PTFE). Another example is a synthetic resin such as acrylic. Alternatively, polypropylene, polyester, polyvinyl fluoride, polyvinyl chloride, or the like can be used. Alternatively, polyamide, polyimide, aramid, epoxy, an inorganic vapor deposition film, paper, or the like can be used. Specifically, the use of a semiconductor substrate, a single crystal substrate, an SOI substrate, or the like enables the manufacture of small-sized transistors with a small variation in characteristics, size, shape, or the like and with high current supply capability. A circuit using such transistors achieves lower power consumption of the circuit or higher integration of the circuit.

Alternatively, a flexible substrate may be used as the substrate, and a transistor or a light-emitting element may be provided directly on the flexible substrate. Still alternatively, a separation layer may be provided between the substrate and the transistor or the light-emitting element. The separation layer can be used when part or the whole of a semiconductor device formed over the separation layer is separated from the substrate and transferred onto another substrate. In such a case, the transistor or the light-emitting element can be transferred to a substrate having low heat resistance or a flexible substrate. For the separation layer, a stack including inorganic films, which are a tungsten film and a silicon oxide film, or an organic resin film of polyimide or the like formed over a substrate can be used, for example.

In other words, a transistor or a light-emitting element may be formed using one substrate, and then transferred to another substrate. Examples of a substrate to which a transistor or a light-emitting element is transferred are, in addition to the above-described substrates over which a transistor or a light-emitting element can be formed, a paper substrate, a cellophane substrate, an aramid film substrate, a polyimide film substrate, a stone substrate, a wood substrate, a cloth substrate (including a natural fiber (e.g., silk, cotton, or hemp), a synthetic fiber (e.g., nylon, polyurethane, or polyester), a regenerated fiber (e.g., acetate, cupra, rayon, or regenerated polyester), or the like), a leather substrate, a rubber substrate, and the like. When such a substrate is used, a transistor with excellent characteristics or a transistor with low power consumption can be formed, a device with high durability or high heat resistance can be provided, or a reduction in weight or thickness can be achieved.

Note that the structures described in this embodiment can be combined with any of the structures described in the other embodiments as appropriate.

Embodiment 5

In this embodiment, examples of a variety of electronic devices and an automobile manufactured using a light-emitting device of one embodiment of the present invention are described.

Examples of the electronic device including the light-emitting device are television devices (also referred to as TV or television receivers), monitors for computers and the like, cameras such as digital cameras and digital video cameras, digital photo frames, cellular phones (also referred to as mobile phones or portable telephone devices), portable game machines, portable information terminals, audio playback devices, large game machines such as pachinko machines, and the like. Specific examples of the electronic devices are illustrated in FIGS. 5A, 5B, 5C, 5D, 5D′-1, and 5D′-2 and FIGS. 6A to 6C.

FIG. 5A illustrates an example of a television device. In a television device 7100, a display portion 7103 is incorporated in a housing 7101. The display portion 7103 can display images and may be a touch panel (an input/output device) including a touch sensor (an input device). Note that the light-emitting device of one embodiment of the present invention can be used for the display portion 7103. In addition, here, the housing 7101 is supported by a stand 7105.

The television device 7100 can be operated with an operation switch of the housing 7101 or a separate remote controller 7110. With operation keys 7109 of the remote controller 7110, channels and volume can be controlled and images displayed on the display portion 7103 can be controlled. Furthermore, the remote controller 7110 may be provided with a display portion 7107 for displaying data output from the remote controller 7110.

Note that the television device 7100 is provided with a receiver, a modem, and the like. With the use of the receiver, general television broadcasts can be received. Moreover, when the television device is connected to a communication network with or without wires via the modem, one-way (from a sender to a receiver) or two-way (between a sender and a receiver or between receivers) information communication can be performed.

FIG. 5B illustrates a computer, which includes a main body 7201, a housing 7202, a display portion 7203, a keyboard 7204, an external connection port 7205, a pointing device 7206, and the like. Note that this computer can be manufactured using the light-emitting device of one embodiment of the present invention for the display portion 7203. The display portion 7203 may be a touch panel (an input/output device) including a touch sensor (an input device).

FIG. 5C illustrates a smart watch, which includes a housing 7302, a display portion 7304, operation buttons 7311 and 7312, a connection terminal 7313, a band 7321, a clasp 7322, and the like.

The display portion 7304 mounted in the housing 7302 serving as a bezel includes a non-rectangular display region. The display portion 7304 can display an icon 7305 indicating time, another icon 7306, and the like. The display portion 7304 may be a touch panel (an input/output device) including a touch sensor (an input device).

The smart watch illustrated in FIG. 5C can have a variety of functions, such as a function of displaying a variety of information (e.g., a still image, a moving image, and a text image) on a display portion, a touch panel function, a function of displaying a calendar, date, time, and the like, a function of controlling processing with a variety of software (programs), a wireless communication function, a function of being connected to a variety of computer networks with a wireless communication function, a function of transmitting and receiving a variety of data with a wireless communication function, and a function of reading a program or data stored in a recording medium and displaying the program or data on a display portion.

The housing 7302 can include a speaker, a sensor (a sensor having a function of measuring force, displacement, position, speed, acceleration, angular velocity, rotational frequency, distance, light, liquid, magnetism, temperature, chemical substance, sound, time, hardness, electric field, current, voltage, electric power, radiation, flow rate, humidity, gradient, oscillation, odor, or infrared rays), a microphone, and the like. Note that the smart watch can be manufactured using the light-emitting device for the display portion 7304.

FIG. 5D illustrates an example of a cellular phone (e.g., smartphone). A cellular phone 7400 includes a housing 7401 provided with a display portion 7402, a microphone 7406, a speaker 7405, a camera 7407, an external connection portion 7404, an operation button 7403, and the like. In the case where a light-emitting device is manufactured by forming the light-emitting element of one embodiment of the present invention over a flexible substrate, the light-emitting device can be used for the display portion 7402 having a curved surface as illustrated in FIG. 5D.

When the display portion 7402 of the cellular phone 7400 illustrated in FIG. 5D is touched with a finger or the like, data can be input to the cellular phone 7400. In addition, operations such as making a call and composing e-mail can be performed by touch on the display portion 7402 with a finger or the like.

There are mainly three screen modes of the display portion 7402. The first mode is a display mode mainly for displaying an image. The second mode is an input mode mainly for inputting data such as characters. The third mode is a display-and-input mode in which two modes of the display mode and the input mode are combined.

For example, in the case of making a call or composing e-mail, a character input mode mainly for inputting characters is selected for the display portion 7402 so that characters displayed on the screen can be input. In this case, it is preferable to display a keyboard or number buttons on almost the entire screen of the display portion 7402.

When a detection device such as a gyroscope sensor or an acceleration sensor is provided inside the cellular phone 7400, display on the screen of the display portion 7402 can be automatically changed by determining the orientation of the cellular phone 7400 (whether the cellular phone is placed horizontally or vertically for a landscape mode or a portrait mode).

The screen modes are changed by touch on the display portion 7402 or operation with the operation button 7403 of the housing 7401. The screen modes can be switched depending on the kind of images displayed on the display portion 7402. For example, when a signal of an image displayed on the display portion is a signal of moving image data, the screen mode is switched to the display mode. When the signal is a signal of text data, the screen mode is switched to the input mode.

Moreover, in the input mode, if a signal detected by an optical sensor in the display portion 7402 is detected and the input by touch on the display portion 7402 is not performed for a certain period, the screen mode may be controlled so as to be changed from the input mode to the display mode.

The display portion 7402 may function as an image sensor. For example, an image of a palm print, a fingerprint, or the like is taken by touch on the display portion 7402 with the palm or the finger, whereby personal authentication can be performed. In addition, by providing a backlight or a sensing light source that emits near-infrared light in the display portion, an image of a finger vein, a palm vein, or the like can be taken.

The light-emitting device can be used for a cellular phone having a structure illustrated in FIG. 5D′-1 or FIG. 5D′-2, which is another structure of the cellular phone (e.g., smartphone).

Note that in the case of the structure illustrated in FIG. 5D′-1 or FIG. 5D′-2, text data, image data, or the like can be displayed on second screens 7502(1) and 7502(2) of housings 7500(1) and 7500(2) as well as first screens 7501(1) and 7501(2). Such a structure enables a user to easily see text data, image data, or the like displayed on the second screens 7502(1) and 7502(2) while the cellular phone is placed in the user's breast pocket.

Another electronic device including a light-emitting device is a foldable portable information terminal illustrated in FIGS. 6A to 6C. FIG. 6A illustrates a portable information terminal 9310 which is opened. FIG. 6B illustrates the portable information terminal 9310 which is being opened or being folded. FIG. 6C illustrates the portable information terminal 9310 which is folded. The portable information terminal 9310 is highly portable when folded. The portable information terminal 9310 is highly browsable when opened because of a seamless large display region.

A display portion 9311 is supported by three housings 9315 joined together by hinges 9313. Note that the display portion 9311 may be a touch panel (an input/output device) including a touch sensor (an input device). By bending the display portion 9311 at a connection portion between two housings 9315 with the use of the hinges 9313, the portable information terminal 9310 can be reversibly changed in shape from an opened state to a folded state. The light-emitting device of one embodiment of the present invention can be used for the display portion 9311. A display region 9312 in the display portion 9311 is a display region that is positioned at a side surface of the portable information terminal 9310 which is folded. On the display region 9312, information icons, file shortcuts of frequently used applications or programs, and the like can be displayed, and confirmation of information and start of application and the like can be smoothly performed.

FIGS. 7A and 7B illustrate an automobile including a light-emitting device. The light-emitting device can be incorporated in the automobile, and specifically, can be included in lights 5101 (including lights of the rear part of the car), a wheel cover 5102, a part or whole of a door 5103, or the like on the outer side of the automobile which is illustrated in FIG. 7A. The light-emitting device can also be included in a display portion 5104, a steering wheel 5105, a gear lever 5106, a seat 5107, an inner rearview mirror 5108, or the like on the inner side of the automobile which is illustrated in FIG. 7B, or in a part of a glass window.

As described above, the electronic devices and automobiles can be obtained using the light-emitting device of one embodiment of the present invention. Note that the light-emitting device can be used for electronic devices and automobiles in a variety of fields without being limited to those described in this embodiment.

Note that the structures described in this embodiment can be combined with any of the structures described in the other embodiments as appropriate.

Embodiment 6

In this embodiment, a structure of a lighting device fabricated using the light-emitting element of one embodiment of the present invention is described with reference to FIGS. 8A to 8D.

FIGS. 8A to 8D are examples of cross-sectional views of lighting devices. FIGS. 8A and 8B illustrate bottom-emission lighting devices in which light is extracted from the substrate side, and FIGS. 8C and 8D illustrate top-emission lighting devices in which light is extracted from the sealing substrate side.

A lighting device 4000 illustrated in FIG. 8A includes a light-emitting element 4002 over a substrate 4001. In addition, the lighting device 4000 includes a substrate 4003 with unevenness on the outside of the substrate 4001. The light-emitting element 4002 includes a first electrode 4004, an EL layer 4005, and a second electrode 4006.

The first electrode 4004 is electrically connected to an electrode 4007, and the second electrode 4006 is electrically connected to an electrode 4008. In addition, an auxiliary wiring 4009 electrically connected to the first electrode 4004 may be provided. Note that an insulating layer 4010 is formed over the auxiliary wiring 4009.

The substrate 4001 and a sealing substrate 4011 are bonded to each other with a sealant 4012. A desiccant 4013 is preferably provided between the sealing substrate 4011 and the light-emitting element 4002. The substrate 4003 has the unevenness illustrated in FIG. 8A, whereby the extraction efficiency of light emitted from the light-emitting element 4002 can be increased.

Instead of the substrate 4003, a diffusion plate 4015 may be provided on the outside of the substrate 4001 as in a lighting device 4100 illustrated in FIG. 8B.

A lighting device 4200 illustrated in FIG. 8C includes a light-emitting element 4202 over a substrate 4201. The light-emitting element 4202 includes a first electrode 4204, an EL layer 4205, and a second electrode 4206.

The first electrode 4204 is electrically connected to an electrode 4207, and the second electrode 4206 is electrically connected to an electrode 4208. An auxiliary wiring 4209 electrically connected to the second electrode 4206 may be provided. An insulating layer 4210 may be provided under the auxiliary wiring 4209.

The substrate 4201 and a sealing substrate 4211 with unevenness are bonded to each other with a sealant 4212. A barrier film 4213 and a planarization film 4214 may be provided between the sealing substrate 4211 and the light-emitting element 4202. The sealing substrate 4211 has the unevenness illustrated in FIG. 8C, whereby the extraction efficiency of light emitted from the light-emitting element 4202 can be increased.

Instead of the sealing substrate 4211, a diffusion plate 4215 may be provided over the light-emitting element 4202 as in a lighting device 4300 illustrated in FIG. 8D.

Note that the EL layers 4005 and 4205 in this embodiment can include the organometallic complex of one embodiment of the present invention. In that case, a lighting device with low power consumption can be provided.

Note that the structures described in this embodiment can be combined with any of the structures described in the other embodiments as appropriate.

Embodiment 7

In this embodiment, examples of a lighting device to which the light-emitting device of one embodiment of the present invention is applied are described with reference to FIG. 9.

FIG. 9 illustrates an example in which the light-emitting device is used as an indoor lighting device 8001. Since the light-emitting device can have a large area, it can be used for a lighting device having a large area. In addition, with the use of a housing with a curved surface, a lighting device 8002 in which a light-emitting region has a curved surface can also be obtained. A light-emitting element included in the light-emitting device described in this embodiment is in a thin film form, which allows the housing to be designed more freely. Thus, the lighting device can be elaborately designed in a variety of ways. In addition, a wall of the room may be provided with a lighting device 8003.

Besides the above examples, when the light-emitting device is used as part of furniture in a room, a lighting device that functions as the furniture can be obtained.

As described above, a variety of lighting devices that include the light-emitting device can be obtained. Note that these lighting devices are also embodiments of the present invention.

The structures described in this embodiment can be combined with any of the structures described in the other embodiments as appropriate.

Embodiment 8

In this embodiment, touch panels including the light-emitting element of one embodiment of the present invention or the light-emitting device of one embodiment of the present invention are described with reference to FIGS. 10A and 10B, FIGS. 11A and 11B, FIGS. 12A and 12B, FIGS. 13A and 13B, and FIG. 14.

FIGS. 10A and 10B are perspective views of a touch panel 2000. Note that FIGS. 10A and 10B illustrate only main components of the touch panel 2000 for simplicity.

The touch panel 2000 includes a display panel 2501 and a touch sensor 2595 (see FIG. 10B). The touch panel 2000 includes a substrate 2510, a substrate 2570, and a substrate 2590.

The display panel 2501 includes, over the substrate 2510, a plurality of pixels and a plurality of wirings 2511 through which signals are supplied to the pixels. The plurality of wirings 2511 are led to a peripheral portion of the substrate 2510, and parts of the plurality of wirings 2511 form a terminal 2519. The terminal 2519 is electrically connected to an FPC 2509(1).

The substrate 2590 includes the touch sensor 2595 and a plurality of wirings 2598 electrically connected to the touch sensor 2595. The plurality of wirings 2598 are led to a peripheral portion of the substrate 2590, and parts of the plurality of wirings 2598 form a terminal 2599. The terminal 2599 is electrically connected to an FPC 2509(2). Note that in FIG. 10B, electrodes, wirings, and the like of the touch sensor 2595 provided on the back side of the substrate 2590 (the side facing the substrate 2510) are indicated by solid lines for clarity.

As the touch sensor 2595, a capacitive touch sensor can be used, for example. Examples of the capacitive touch sensor include a surface capacitive touch sensor, a projected capacitive touch sensor, and the like.

Examples of the projected capacitive touch sensor are a self-capacitive touch sensor, a mutual capacitive touch sensor, and the like, which differ mainly in the driving method. The use of a mutual capacitive type is preferable because multiple points can be sensed simultaneously.

First, an example of using a projected capacitive touch sensor is described below with reference to FIG. 10B. Note that in the case of a projected capacitive touch sensor, a variety of sensors that can sense proximity or touch of a sensing target such as a finger can be used.

The projected capacitive touch sensor 2595 includes electrodes 2591 and electrodes 2592. The electrodes 2591 are electrically connected to any of the plurality of wirings 2598, and the electrodes 2592 are electrically connected to any of the other wirings 2598. The electrodes 2592 each have a shape of a plurality of quadrangles arranged in one direction with one corner of a quadrangle connected to one corner of another quadrangle with a wiring 2594, as illustrated in FIGS. 10A and 10B. In the same manner, the electrodes 2591 each have a shape of a plurality of quadrangles arranged with one corner of a quadrangle connected to one corner of another quadrangle; however, the direction in which the electrodes 2591 are connected is a direction crossing the direction in which the electrodes 2592 are connected. Note that the direction in which the electrodes 2591 are connected and the direction in which the electrodes 2592 are connected are not necessarily perpendicular to each other, and the electrodes 2591 may be arranged to intersect with the electrodes 2592 at an angle greater than 0° and less than 90°.

The intersecting area of the electrode 2592 and the wiring 2594 is preferably as small as possible. Such a structure allows a reduction in the area of a region where the electrodes are not provided, reducing variation in transmittance. As a result, variation in luminance of light passing through the touch sensor 2595 can be reduced.

Note that the shapes of the electrodes 2591 and the electrodes 2592 are not limited thereto and can be any of a variety of shapes. For example, the plurality of electrodes 2591 may be provided so that a space between the electrodes 2591 is reduced as much as possible, and the plurality of electrodes 2592 may be provided with an insulating layer located between the electrodes 2591 and 2592. In this case, it is preferable to provide, between two adjacent electrodes 2592, a dummy electrode electrically insulated from these electrodes because the area of regions having different transmittances can be reduced.

Next, the touch panel 2000 will be described in detail with reference to FIGS. 11A and 11B. FIGS. 11A and 11B correspond to cross-sectional views taken along dashed-dotted line X1-X2 in FIG. 10A.

The touch panel 2000 includes the touch sensor 2595 and the display panel 2501.

The touch sensor 2595 includes the electrodes 2591 and the electrodes 2592 provided in a staggered arrangement in contact with the substrate 2590, an insulating layer 2593 covering the electrodes 2591 and the electrodes 2592, and the wiring 2594 that electrically connects the adjacent electrodes 2591 to each other. Between the adjacent electrodes 2591, the electrode 2592 is provided.

The electrodes 2591 and the electrodes 2592 can be formed using a light-transmitting conductive material. As a light-transmitting conductive material, a conductive oxide such as indium oxide, indium tin oxide, indium zinc oxide, zinc oxide, or zinc oxide to which gallium is added can be used. A graphene compound may be used as well. When a graphene compound is used, it can be formed, for example, by reducing a graphene oxide film. As a reducing method, a method with application of heat, a method with laser irradiation, or the like can be employed.

For example, the electrodes 2591 and 2592 can be formed by depositing a light-transmitting conductive material on the substrate 2590 by a sputtering method and then removing an unneeded portion by any of various patterning techniques such as photolithography.

Examples of a material for the insulating layer 2593 include a resin such as an acrylic resin or an epoxy resin, a resin having a siloxane bond, and an inorganic insulating material such as silicon oxide, silicon oxynitride, or aluminum oxide.

The adjacent electrodes 2591 are electrically connected to each other with the wiring 2594 formed in part of the insulating layer 2593. Note that a material for the wiring 2594 preferably has higher conductivity than materials for the electrodes 2591 and 2592 to reduce electrical resistance.

The wiring 2598 is electrically connected to any of the electrodes 2591 and 2592. Part of the wiring 2598 functions as a terminal. For the wiring 2598, a metal material such as aluminum, gold, platinum, silver, nickel, titanium, tungsten, chromium, molybdenum, iron, cobalt, copper, or palladium or an alloy material containing any of these metal materials can be used.

Through the terminal 2599, the wiring 2598 and the FPC 2509(2) are electrically connected to each other. The terminal 2599 can be formed using any of various kinds of anisotropic conductive films (ACF), anisotropic conductive pastes (ACP), and the like.

An adhesive layer 2597 is provided in contact with the wiring 2594. That is, the touch sensor 2595 is attached to the display panel 2501 so that they overlap with each other with the adhesive layer 2597 provided therebetween. Note that the substrate 2570 as illustrated in FIG. 11A may be provided over the surface of the display panel 2501 that is in contact with the adhesive layer 2597; however, the substrate 2570 is not always needed.

The adhesive layer 2597 has a light-transmitting property. For example, a thermosetting resin or an ultraviolet curable resin can be used; specifically, a resin such as an acrylic-based resin, a urethane-based resin, an epoxy-based resin, or a siloxane-based resin can be used.

The display panel 2501 in FIG. 11A includes, between the substrate 2510 and the substrate 2570, a plurality of pixels arranged in a matrix and a driver circuit. Each pixel includes a light-emitting element and a pixel circuit driving the light-emitting element.

In FIG. 11A, a pixel 2502R is shown as an example of the pixel of the display panel 2501, and a scan line driver circuit 2503 g is shown as an example of the driver circuit.

The pixel 2502R includes a light-emitting element 2550R and a transistor 2502 t that can supply electric power to the light-emitting element 2550R.

The transistor 2502 t is covered with an insulating layer 2521. The insulating layer 2521 has a function of providing a flat surface by covering unevenness caused by the transistor and the like that have been already formed. The insulating layer 2521 may serve also as a layer for preventing diffusion of impurities. That is preferable because a reduction in the reliability of the transistor or the like due to diffusion of impurities can be prevented.

The light-emitting element 2550R is electrically connected to the transistor 2502 t through a wiring. It is one electrode of the light-emitting element 2550R that is directly connected to the wiring. An end portion of the one electrode of the light-emitting element 2550R is covered with an insulator 2528.

The light-emitting element 2550R includes an EL layer between a pair of electrodes. A coloring layer 2567R is provided to overlap with the light-emitting element 2550R, and part of light emitted from the light-emitting element 2550R is transmitted through the coloring layer 2567R and extracted in the direction indicated by an arrow in the drawing. A light-blocking layer 2567BM is provided at an end portion of the coloring layer, and a sealing layer 2560 is provided between the light-emitting element 2550R and the coloring layer 2567R.

Note that when the sealing layer 2560 is provided on the side from which light from the light-emitting element 2550R is extracted, the sealing layer 2560 preferably has a light-transmitting property. The sealing layer 2560 preferably has a higher refractive index than the air.

The scan line driver circuit 2503 g includes a transistor 2503 t and a capacitor 2503 c. Note that the driver circuit and the pixel circuits can be formed in the same process over the same substrate. Thus, in a manner similar to that of the transistor 2502 t in the pixel circuit, the transistor 2503 t in the driver circuit (the scan line driver circuit 2503 g) is also covered with the insulating layer 2521.

The wirings 2511 through which a signal can be supplied to the transistor 2503 t are provided. The terminal 2519 is provided in contact with the wiring 2511. The terminal 2519 is electrically connected to the FPC 2509(1), and the FPC 2509(1) has a function of supplying signals such as an image signal and a synchronization signal. Note that a printed wiring board (PWB) may be attached to the FPC 2509(1).

Although the case where the display panel 2501 illustrated in FIG. 11A includes a bottom-gate transistor is described, the structure of the transistor is not limited thereto, and any of transistors with various structures can be used. In each of the transistors 2502 t and 2503 t illustrated in FIG. 11A, a semiconductor layer containing an oxide semiconductor can be used for a channel region. Alternatively, a semiconductor layer containing amorphous silicon or a semiconductor layer containing polycrystalline silicon that is obtained by crystallization process such as laser annealing can be used for a channel region.

FIG. 11B illustrates the structure of the display panel 2501 that includes a top-gate transistor instead of the bottom-gate transistor illustrated in FIG. 11A. The kind of the semiconductor layer that can be used for the channel region does not depend on the structure of the transistor.

In the touch panel 2000 illustrated in FIG. 11A, an anti-reflection layer 2567 p overlapping with at least the pixel is preferably provided on a surface of the touch panel on the side from which light from the pixel is extracted, as illustrated in FIG. 11A. As the anti-reflection layer 2567 p, a circular polarizing plate or the like can be used.

For the substrates 2510, 2570, and 2590 in FIG. 11A, for example, a flexible material having a vapor permeability of 1×10⁻⁵ g/(m²·day) or lower, preferably 1×10⁻⁶ g/(m²·day) or lower, can be favorably used. Alternatively, it is preferable to use the materials that make these substrates have substantially the same coefficient of thermal expansion. For example, the coefficients of linear expansion of the materials are 1×10⁻³/K or lower, preferably 5×10⁻⁵/K or lower, and further preferably 1×10⁻⁵/K or lower.

Next, a touch panel 2000′ having a structure different from that of the touch panel 2000 illustrated in FIGS. 11A and 11B is described with reference to FIGS. 12A and 12B. It can be used as a touch panel as well as the touch panel 2000.

FIGS. 12A and 12B are cross-sectional views of the touch panel 2000′. In the touch panel 2000′ illustrated in FIGS. 12A and 12B, the position of the touch sensor 2595 relative to the display panel 2501 is different from that in the touch panel 2000 illustrated in FIGS. 11A and 11B. Only different structures are described below, and the above description of the touch panel 2000 can be referred to for the other similar structures.

The coloring layer 2567R overlaps with the light-emitting element 2550R. Light from the light-emitting element 2550R illustrated in FIG. 12A is emitted to the side where the transistor 2502 t is provided. That is, (part of) light emitted from the light-emitting element 2550R passes through the coloring layer 2567R and is extracted in the direction indicated by an arrow in FIG. 12A. Note that the light-blocking layer 2567BM is provided at an end portion of the coloring layer 2567R.

The touch sensor 2595 is provided on the transistor 2502 t side (the far side from the light-emitting element 2550R) of the display panel 2501 (see FIG. 12A).

The adhesive layer 2597 is in contact with the substrate 2510 of the display panel 2501 and attaches the display panel 2501 and the touch sensor 2595 to each other in the structure illustrated in FIG. 12A. The substrate 2510 is not necessarily provided between the display panel 2501 and the touch sensor 2595 that are attached to each other by the adhesive layer 2597.

As in the touch panel 2000, transistors with a variety of structures can be used for the display panel 2501 in the touch panel 2000′. Although a bottom-gate transistor is used in FIG. 12A, a top-gate transistor may be used as illustrated in FIG. 12B.

An example of a driving method of the touch panel is described with reference to FIGS. 13A and 13B.

FIG. 13A is a block diagram illustrating the structure of a mutual capacitive touch sensor. FIG. 13A illustrates a pulse voltage output circuit 2601 and a current sensing circuit 2602. Note that in FIG. 13A, six wirings X1 to X6 represent electrodes 2621 to which a pulse voltage is applied, and six wirings Y1 to Y6 represent electrodes 2622 that detect changes in current. FIG. 13A also illustrates capacitors 2603 that are each formed in a region where the electrodes 2621 and 2622 overlap with each other. Note that functional replacement between the electrodes 2621 and 2622 is possible.

The pulse voltage output circuit 2601 is a circuit for sequentially applying a pulse voltage to the wirings X1 to X6. By application of a pulse voltage to the wirings X1 to X6, an electric field is generated between the electrodes 2621 and 2622 of the capacitor 2603. When the electric field between the electrodes is shielded, for example, a change occurs in the capacitor 2603 (mutual capacitance). The approach or contact of a sensing target can be sensed by utilizing this change.

The current sensing circuit 2602 is a circuit for detecting changes in current flowing through the wirings Y1 to Y6 that are caused by the change in mutual capacitance in the capacitor 2603. No change in current value is detected in the wirings Y1 to Y6 when there is no approach or contact of a sensing target, whereas a decrease in current value is detected when mutual capacitance is decreased owing to the approach or contact of a sensing target. Note that an integrator circuit or the like is used for sensing of current values.

FIG. 13B is a timing chart showing input and output waveforms in the mutual capacitive touch sensor illustrated in FIG. 13A. In FIG. 13B, sensing of a sensing target is performed in all the rows and columns in one frame period. FIG. 13B shows a period when a sensing target is not sensed (not touched) and a period when a sensing target is sensed (touched). Sensed current values of the wirings Y1 to Y6 are shown as the waveforms of voltage values.

A pulse voltage is sequentially applied to the wirings X1 to X6, and the waveforms of the wirings Y1 to Y6 change in accordance with the pulse voltage. When there is no approach or contact of a sensing target, the waveforms of the wirings Y1 to Y6 change uniformly in accordance with changes in the voltages of the wirings X1 to X6. The current value is decreased at the point of approach or contact of a sensing target and accordingly the waveform of the voltage value changes. By detecting a change in mutual capacitance in this manner, the approach or contact of a sensing target can be sensed.

Although FIG. 13A illustrates a passive-type touch sensor in which only the capacitor 2603 is provided at the intersection of wirings as a touch sensor, an active-type touch sensor including a transistor and a capacitor may be used. FIG. 14 illustrates an example of a sensor circuit included in an active-type touch sensor.

The sensor circuit in FIG. 14 includes the capacitor 2603 and transistors 2611, 2612, and 2613.

A signal G2 is input to a gate of the transistor 2613. A voltage VRES is applied to one of a source and a drain of the transistor 2613, and one electrode of the capacitor 2603 and a gate of the transistor 2611 are electrically connected to the other of the source and the drain of the transistor 2613. One of a source and a drain of the transistor 2611 is electrically connected to one of a source and a drain of the transistor 2612, and a voltage VSS is applied to the other of the source and the drain of the transistor 2611. A signal G1 is input to a gate of the transistor 2612, and a wiring ML is electrically connected to the other of the source and the drain of the transistor 2612. The voltage VSS is applied to the other electrode of the capacitor 2603.

Next, the operation of the sensor circuit in FIG. 14 is described. First, a potential for turning on the transistor 2613 is supplied as the signal G2, and a potential with respect to the voltage VRES is thus applied to a node n connected to the gate of the transistor 2611. Then, a potential for turning off the transistor 2613 is applied as the signal G2, whereby the potential of the node n is maintained. Then, mutual capacitance of the capacitor 2603 changes owing to the approach or contact of a sensing target such as a finger, and accordingly the potential of the node n is changed from VRES.

In reading operation, a potential for turning on the transistor 2612 is supplied as the signal G1. A current flowing through the transistor 2611, that is, a current flowing through the wiring ML is changed in accordance with the potential of the node n. By sensing this current, the approach or contact of a sensing target can be sensed.

In each of the transistors 2611, 2612, and 2613, an oxide semiconductor layer is preferably used as a semiconductor layer in which a channel region is formed. In particular, it is preferable to use such a transistor as the transistor 2613 because the potential of the node n can be held for a long time and the frequency of operation of resupplying VRES to the node n (refresh operation) can be reduced.

Note that the structures described in this embodiment can be combined with any of the structures described in the other embodiments as appropriate.

Embodiment 9

In this embodiment, as a display device including the light-emitting element of one embodiment of the present invention, a display device which includes a reflective liquid crystal element and a light-emitting element and is capable of performing display both in a transmissive mode and a reflective mode is described with reference to FIGS. 15A, 15B1, and 15B2, FIG. 16, and FIG. 17. Such a display device can also be referred to as an emissive OLED and reflective LC hybrid display (ER-hybrid display).

The display device described in this embodiment can be driven with extremely low power consumption for display using the reflective mode in a bright place such as outdoors. Meanwhile, in a dark place such as indoors or at night, an image can be displayed at an optimal luminance with the use of the transmissive mode. Thus, by combination of these modes, the display device can display an image with lower power consumption and higher contrast than a conventional display panel.

As an example of the display device of this embodiment, description is made on a display device in which a liquid crystal element provided with a reflective electrode and a light-emitting element are stacked and an opening in the reflective electrode is provided in a position overlapping with the light-emitting element. Visible light is reflected by the reflective electrode in the reflective mode and light emitted from the light-emitting element is emitted through the opening in the reflective electrode in the transmissive mode. Note that transistors used for driving these elements (the liquid crystal element and the light-emitting element) are preferably formed on the same plane. It is preferable that the liquid crystal element and the light-emitting element be stacked with an insulating layer therebetween.

FIG. 15A is a block diagram illustrating a display device described in this embodiment. A display device 500 includes a circuit (G) 501, a circuit (S) 502, and a display portion 503. In the display portion 503, a plurality of pixels 504 are arranged in an R direction and a C direction in a matrix. A plurality of wirings G1, a plurality of wirings G2, a plurality of wirings ANO, and a plurality of wirings CSCOM are electrically connected to the circuit (G) 501. These wirings are also electrically connected to the plurality of pixels 504 arranged in the R direction. A plurality of wirings S1 and a plurality of wirings S2 are electrically connected to the circuit (S) 502, and these wirings are also electrically connected to the plurality of pixels 504 arranged in the C direction.

Each of the plurality of pixels 504 includes a liquid crystal element and a light-emitting element. The liquid crystal element and the light-emitting element include portions overlapping with each other.

FIG. 15B1 shows the shape of a conductive film 505 serving as a reflective electrode of the liquid crystal element included in the pixel 504. Note that an opening 507 is provided in a position 506 which is part of the conductive film 505 and which overlaps with the light-emitting element. That is, light emitted from the light-emitting element is emitted through the opening 507.

The pixels 504 in FIG. 15B1 are arranged such that adjacent pixels 504 in the R direction exhibit different colors. Furthermore, the openings 507 are provided so as not to be arranged in a line in the R direction. Such arrangement has an effect of suppressing crosstalk between the light-emitting elements of adjacent pixels 504.

The opening 507 can have a polygonal shape, a quadrangular shape, an elliptical shape, a circular shape, a cross shape, a stripe shape, or a slit-like shape, for example

FIG. 15B2 illustrates another example of the arrangement of the conductive films 505.

The ratio of the opening 507 to the total area of the conductive film 505 (excluding the opening 507) affects the display of the display device. That is, a problem is caused in that as the area of the opening 507 is larger, the display using the liquid crystal element becomes darker; in contrast, as the area of the opening 507 is smaller, the display using the light-emitting element becomes darker. Furthermore, in addition to the problem of the ratio of the opening, a small area of the opening 507 itself also causes a problem in that extraction efficiency of light emitted from the light-emitting element is decreased. The ratio of the opening 507 to the total area of the conductive film 505 (excluding the opening 507) is preferably 5% or more and 60% or less for maintaining display quality at the time of combination of the liquid crystal element and the light-emitting element.

Next, an example of a circuit configuration of the pixel 504 is described with reference to FIG. 16. FIG. 16 shows two adjacent pixels 504.

The pixel 504 includes a transistor SW1, a capacitor C1, a liquid crystal element 510, a transistor SW2, a transistor M, a capacitor C2, a light-emitting element 511, and the like. Note that these components are electrically connected to any of the wiring G1, the wiring G2, the wiring ANO, the wiring CSCOM, the wiring S1, and the wiring S2 in the pixel 504. The liquid crystal element 510 and the light-emitting element 511 are electrically connected to a wiring VCOM1 and a wiring VCOM2, respectively.

A gate of the transistor SW1 is connected to the wiring G1. One of a source and a drain of the transistor SW1 is connected to the wiring S1, and the other of the source and the drain is connected to one electrode of the capacitor C1 and one electrode of the liquid crystal element 510. The other electrode of the capacitor C1 is connected to the wiring CSCOM. The other electrode of the liquid crystal element 510 is connected to the wiring VCOM1.

A gate of the transistor SW2 is connected to the wiring G2. One of a source and a drain of the transistor SW2 is connected to the wiring S2, and the other of the source and the drain is connected to one electrode of the capacitor C2 and a gate of the transistor M. The other electrode of the capacitor C2 is connected to one of a source and a drain of the transistor M and the wiring ANO. The other of the source and the drain of the transistor M is connected to one electrode of the light-emitting element 511. Furthermore, the other electrode of the light-emitting element 511 is connected to the wiring VCOM2.

Note that the transistor M includes two gates between which a semiconductor is provided and which are electrically connected to each other. With such a structure, the amount of current flowing through the transistor M can be increased.

The on/off state of the transistor SW1 is controlled by a signal from the wiring G1. A predetermined potential is supplied from the wiring VCOM1. Furthermore, orientation of liquid crystals of the liquid crystal element 510 can be controlled by a signal from the wiring S1. A predetermined potential is supplied from the wiring CSCOM.

The on/off state of the transistor SW2 is controlled by a signal from the wiring G2. By the difference between the potentials applied from the wiring VCOM2 and the wiring ANO, the light-emitting element 511 can emit light. Furthermore, the conduction state of the transistor M can be controlled by a signal from the wiring S2.

Accordingly, in the structure of this embodiment, in the case of the reflective mode, the liquid crystal element 510 is controlled by the signals supplied from the wiring G1 and the wiring S1 and optical modulation is utilized, whereby display can be performed. In the case of the transmissive mode, the light-emitting element 511 can emit light when the signals are supplied from the wiring G2 and the wiring S2. In the case where both modes are performed at the same time, desired driving can be performed on the basis of the signals from the wiring G1, the wiring G2, the wiring S1, and the wiring S2.

Next, specific description is given with reference to FIG. 17, a schematic cross-sectional view of the display device 500 described in this embodiment.

The display device 500 includes a light-emitting element 523 and a liquid crystal element 524 between substrates 521 and 522. Note that the light-emitting element 523 and the liquid crystal element 524 are formed with an insulating layer 525 positioned therebetween. That is, the light-emitting element 523 is positioned between the substrate 521 and the insulating layer 525, and the liquid crystal element 524 is positioned between the substrate 522 and the insulating layer 525.

A transistor 515, a transistor 516, a transistor 517, a coloring layer 528, and the like are provided between the insulating layer 525 and the light-emitting element 523.

A bonding layer 529 is provided between the substrate 521 and the light-emitting element 523. The light-emitting element 523 includes a conductive layer 530 serving as one electrode, an EL layer 531, and a conductive layer 532 serving as the other electrode which are stacked in this order over the insulating layer 525. In the light-emitting element 523 that is a bottom emission light-emitting element, the conductive layer 532 and the conductive layer 530 contain a material that reflects visible light and a material that transmits visible light, respectively. Light emitted from the light-emitting element 523 is transmitted through the coloring layer 528 and the insulating layer 525 and then transmitted through the liquid crystal element 524 via an opening 533, thereby being emitted to the outside of the substrate 522.

In addition to the liquid crystal element 524, a coloring layer 534, a light-blocking layer 535, an insulating layer 546, a structure 536, and the like are provided between the insulating layer 525 and the substrate 522. The liquid crystal element 524 includes a conductive layer 537 serving as one electrode, a liquid crystal 538, a conductive layer 539 serving as the other electrode, alignment films 540 and 541, and the like. Note that the liquid crystal element 524 is a reflective liquid crystal element and the conductive layer 539 serves as a reflective electrode; thus, the conductive layer 539 is formed using a material with high reflectivity. Furthermore, the conductive layer 537 serves as a transparent electrode, and thus is formed using a material that transmits visible light. The alignment films 540 and 541 are provided on the conductive layers 537 and 539 and in contact with the liquid crystal 538. The insulating layer 546 is provided so as to cover the coloring layer 534 and the light-blocking layer 535 and serves as an overcoat. Note that the alignment films 540 and 541 are not necessarily provided.

The opening 533 is provided in part of the conductive layer 539. A conductive layer 543 is provided in contact with the conductive layer 539. Since the conductive layer 543 has a light-transmitting property, a material transmitting visible light is used for the conductive layer 543.

The structure 536 serves as a spacer that prevents the substrate 522 from coming closer to the insulating layer 525 than required. The structure 536 is not necessarily provided.

One of a source and a drain of the transistor 515 is electrically connected to the conductive layer 530 in the light-emitting element 523. For example, the transistor 515 corresponds to the transistor M in FIG. 16.

One of a source and a drain of the transistor 516 is electrically connected to the conductive layer 539 and the conductive layer 543 in the liquid crystal element 524 through a terminal portion 518. That is, the terminal portion 518 has a function of electrically connecting the conductive layers provided on both surfaces of the insulating layer 525. The transistor 516 corresponds to the transistor SW1 in FIG. 16.

A terminal portion 519 is provided in a region where the substrates 521 and 522 do not overlap with each other. Similarly to the terminal portion 518, the terminal portion 519 electrically connects the conductive layers provided on both surfaces of the insulating layer 525. The terminal portion 519 is electrically connected to a conductive layer obtained by processing the same conductive film as the conductive layer 543. Thus, the terminal portion 519 and an FPC 544 can be electrically connected to each other through a connection layer 545.

A connection portion 547 is provided in part of a region where a bonding layer 542 is provided. In the connection portion 547, the conductive layer obtained by processing the same conductive film as the conductive layer 543 and part of the conductive layer 537 are electrically connected with a connector 548. Accordingly, a signal or a potential input from the FPC 544 can be supplied to the conductive layer 537 through the connector 548.

The structure 536 is provided between the conductive layer 537 and the conductive layer 543. The structure 536 has a function of maintaining a cell gap of the liquid crystal element 524.

As the conductive layer 543, a metal oxide, a metal nitride, or an oxide such as an oxide semiconductor whose resistance is reduced is preferably used. In the case of using an oxide semiconductor, a material in which at least one of the concentrations of hydrogen, boron, phosphorus, nitrogen, and other impurities and the number of oxygen vacancies is made to be higher than those in a semiconductor layer of a transistor is used for the conductive layer 543.

Note that the structures described in this embodiment can be combined with any of the structures described in the other embodiments as appropriate.

Embodiment 10

In this embodiment, a light-emitting element of one embodiment of the present invention is described. The light-emitting element described in this embodiment has a structure different from that described in Embodiment 2. An element structure and a manufacturing method of the light-emitting element are described with reference to FIGS. 18A and 18B. For the portions similar to those in Embodiment 2, the description of Embodiment 2 can be referred to and description is omitted.

The light-emitting element described in this embodiment has a structure in which an EL layer 3202 including a light-emitting layer 3213 is sandwiched between a pair of electrodes (a cathode 3201 and an anode 3203) formed over a substrate 3200. The EL layer 3202 can be formed by stacking a light-emitting layer, a hole-injection layer, a hole-transport layer, an electron-injection layer, an electron-transport layer, and the like as in the EL layer described in Embodiment 2.

In this embodiment, as shown in FIG. 18A, description is made on the light-emitting element having a structure in which the EL layer 3202 including an electron-injection layer 3214, the light-emitting layer 3213, a hole-transport layer 3215, and a hole-injection layer 3216 are formed over the cathode 3201 in this order over the substrate 3200 and the anode 3203 is formed over the hole-injection layer 3216. Here, although an electron-transport layer is not provided, the electron-injection layer 3214 can serve as the electron-transport layer with a material having a high electron-transport property.

In the above-described light-emitting element, current flows because of a potential difference applied between the cathode 3201 and the anode 3203, and holes and electrons recombine in the EL layer 3202, whereby light is emitted. Then, this light emission is extracted to the outside through one or both of the cathode 3201 and the anode 3203. Therefore, one or both of the cathode 3201 and the anode 3203 are electrodes having light-transmitting properties; light can be extracted through the electrode having a light-transmitting property.

In the light-emitting element described in this embodiment, end portions of the cathode 3201 are covered with an insulator 3217 as shown in FIG. 18A. Note that the insulator 3217 is formed so as to fill a space between adjacent cathodes 3201 (e.g., 3201 a and 3201 b) as shown in FIG. 18B.

As the insulator 3217, an inorganic compound or an organic compound having an insulating property can be used. As the organic compound, a photosensitive resin such as a resist material, e.g., an acrylic resin, a polyimide resin, a fluorine-based resin, or the like can be used. As the inorganic compound, silicon oxide, silicon oxynitride, silicon nitride, or the like can be used, for example. Note that the insulator 3217 preferably has a water-repellent surface. As its treatment method, plasma treatment, chemical treatment (using an alkaline solution or an organic solvent), or the like can be employed.

In this embodiment, the electron-injection layer 3214 formed over the cathode 3201 is formed using a high molecular compound. It is preferable to use a high molecular compound which does not easily dissolve in a nonaqueous solvent and which has a high electron-transport property. Specifically, the electron-injection layer 3214 is formed using an appropriate combination of any of the materials in Embodiment 2 (including not only a high molecular compound but also an alkali metal, an alkaline earth metal, or a compound thereof) which can be used for the electron-injection layer 115 and the electron-transport layer 114. The materials are dissolved in a polar solvent, and the layer is formed by a coating method.

Here, examples of the polar solvent include methanol, ethanol, propanol, isopropanol, butyl alcohol, ethylene glycol, glycerin, and the like.

The light-emitting layer 3213 is formed over the electron-injection layer 3214. The light-emitting layer 3213 is formed by depositing (or applying) ink in which any of the materials (light-emitting substances) in Embodiment 2 which can be used for the light-emitting layer 113 are combined as appropriate and dissolved (or dispersed) in a nonpolar solvent, by a wet method (an ink-jet method or a printing method). Although the electron-injection layer 3214 is shared by light-emitting elements of different emission colors, a material corresponding to an emission color is selected for the light-emitting layer 3213. As the nonpolar solvent, an aromatic-based solvent such as toluene or xylene, or a heteroaromatic-based solvent such as pyridine can be used. Alternatively, a solvent such as hexane, 2-methylhexane, cyclohexane, or chloroform can be used.

As shown in FIG. 18B, the ink for forming the light-emitting layer 3213 is applied from a head portion 3300 of an apparatus for applying a solution (hereinafter referred to as solution application apparatus). Note that the head portion 3300 includes a plurality of spraying portions 3301 a to 3301 c having a function of spraying ink, and piezoelectric elements 3302 a to 3302 c are provided for the spraying portions 3301 a to 3301 c. Furthermore, the spraying portions 3301 a to 3301 c are filled with respective inks 3303 a to 3303 c containing light-emitting substances exhibiting different emission colors.

The inks 3303 a to 3303 c are sprayed from the spraying portions 3301 a to 3301 c, whereby light-emitting layers 3213 a to 3213 c exhibiting different emission colors are formed, respectively.

The hole-transport layer 3215 is formed over the light-emitting layer 3213. The hole-transport layer 3215 can be formed by an appropriate combination of any of the materials in Embodiment 2 which can be used for the hole-transport layer 112. The hole-transport layer 3215 can be formed by a vacuum evaporation method or a coating method. In the case of employing a coating method, the material which is dissolved in a solvent is applied to the light-emitting layer 3213 and the insulator 3217. As a coating method, an ink-jet method, a spin coating method, a printing method, or the like can be used.

The hole-injection layer 3216 is formed over the hole-transport layer 3215. The anode 3203 is formed over the hole-injection layer 3216. They can be formed using an appropriate combination of the materials described in Embodiment 2 by a vacuum evaporation method.

The light-emitting element can be formed through the above steps. Note that in the case of using the organometallic complex of one embodiment of the present invention in the light-emitting layer, phosphorescence due to the organometallic complex is obtained. Thus, the light-emitting element can have higher efficiency than a light-emitting element formed using only fluorescent compounds.

Note that the structures described in this embodiment can be combined with any of the structures described in the other embodiments as appropriate.

Example 1 Synthesis Example 1

In this example is described a method for synthesizing the organometallic complex of one embodiment of the present invention, bis{2-[6-(1,1-dimethylethyl)-4-pyrimidinyl-κN³]phenyl-κC}[2-(2-pyridinyl-κN)phenyl-κC]iridium(III) (abbreviation: [Ir(tBuppm)₂(ppy)]) which is represented by Structural Formula (100) in Embodiment 1. A structure of [Ir(tBuppm)₂(ppy)] is shown below.

First, 4.2 g of di-μ-chloro-tetrakis{2-[6-(1,1-dimethylethyl)-4-pyrimidinyl-κN³]phenyl-κC}diiridium(III) (abbreviation: [Ir(tBuppm)₂Cl]₂) and 420 mL of dichloromethane were put into a three-neck flask, and the atmosphere in the flask was replaced with nitrogen. A mixed solution of 2.5 g of silver trifluoromethanesulfonate and 200 mL of methanol was dripped into the flask, followed by overnight stirring at room temperature. The obtained mixture was filtered through a filter aid in which Celite, neutral silica, and Celite were stacked in this order, and the filtrate was concentrated to give a solid. Then, 2.0 g of 2-phenylpyridine (abbreviation: Hppy) and 80 mL of ethanol were added to the solid, and the mixture was refluxed in a nitrogen atmosphere for 14 hours.

The obtained mixture was filtered, and the residue was purified by flash column chromatography using dichloromethane and hexane in a ratio of 1:1 as a developing solvent. The obtained solution was concentrated, followed by recrystallization from dichloromethane and methanol to give the organometallic complex [Ir(tBuppm)₂(ppy)] as a yellow solid (yield: 13%).

By a train sublimation method, 0.71 g of the obtained yellow solid was purified under a pressure of 2.3 Pa with an argon flow rate of 10 mL/min at 260° C. After the sublimation purification, a yellow solid which was a target substance was obtained in a yield of 86%. The synthesis scheme of the above synthesis method is shown in (a) below.

Analysis results by nuclear magnetic resonance (¹H-NMR) spectroscopy of the target substance (yellow solid) obtained by the above-described synthesis method are shown below. FIG. 19 shows the ¹H-NMR chart. These results reveal that the organometallic complex [Ir(tBuppm)₂(ppy)] represented by Structural Formula (100) was obtained in this synthesis example.

¹H-NMR δ (CDCl₃): 1.36 (s, 9H), 1.38 (s, 9H), 6.78 (d, 1H), 6.83-6.96 (m, 9H), 7.59-7.64 (m, 2H), 7.68 (d, 1H), 7.76-7.79 (m, 4H), 7.89 (d, 1H), 8.14 (s, 1H), 8.24 (s, 1H).

Next, an ultraviolet-visible absorption spectrum (hereinafter, simply referred to as an “absorption spectrum”) of a dichloromethane solution of [Ir(tBuppm)₂(ppy)] and an emission spectrum thereof were measured. The measurement of the absorption spectrum was conducted at room temperature, for which an ultraviolet and visible spectrophotometer (V550 type manufactured by JASCO Corporation) was used and the dichloromethane solution (0.092 mmol/L) was put in a quartz cell. In addition, the measurement of the emission spectrum was conducted at room temperature, for which a fluorescence spectrophotometer (FS920 manufactured by Hamamatsu Photonics K.K.) was used and the degassed dichloromethane solution (0.092 mmol/L) was put in a quartz cell.

Measurement results of the obtained absorption and emission spectra are shown in FIG. 20, in which the horizontal axis represents wavelength and the vertical axes represent absorption intensity and emission intensity. In FIG. 20, two solid lines are shown; a thin line represents the absorption spectrum, and a thick line represents the emission spectrum. The absorption spectrum in FIG. 20 is the results obtained in such a way that the absorbance measured by putting only dichloromethane in a quartz cell was subtracted from the absorbance measured by putting the dichloromethane solution (0.092 mmol/L) in a quartz cell.

As shown in FIG. 20, the organometallic complex [Ir(tBuppm)₂(ppy)] has an emission peak at 554 nm, and yellow light emission was observed from the dichloromethane solution.

Next, [Ir(tBuppm)₂(ppy)] obtained in this example was subjected to a mass spectrometry (MS) analysis by liquid chromatography-mass spectrometry (LC-MS).

In the LC-MS analysis, liquid chromatography (LC) separation was carried out with ACQUITY UPLC (registered trademark) manufactured by Waters Corporation, and mass spectrometry (MS) was carried out with Xevo G2 Tof MS manufactured by Waters Corporation. ACQUITY UPLC BEH C8 (2.1×100 mm, 1.7 μm) was used as a column for the LC separation, and the column temperature was set to 40° C. Acetonitrile was used for Mobile Phase A and a 0.1% aqueous solution of formic acid was used for Mobile Phase B. Furthermore, a sample was prepared in such a manner that [Ir(tBuppm)₂(ppy)] was dissolved in chloroform at a given concentration and the mixture was diluted with acetonitrile. The injection amount was 5.0 μL.

In the MS analysis, ionization was carried out by an electrospray ionization (ESI) method. At this time, the capillary voltage and the sample cone voltage were set to 3.0 kV and 50 V, respectively, and detection was performed in a positive mode. A component with m/z of 770.28 which underwent the ionization under the above-described conditions was collided with an argon gas in a collision cell to dissociate into product ions. Energy (collision energy) for the collision with argon was set to 50 eV. The measurement mass range was set to m/z=100 to 1200. The detection results of the dissociated product ions by time-of-flight (TOF) MS are shown in FIG. 21.

FIG. 21 shows that product ions of [Ir(tBuppm)₂(ppy)] are mainly detected around m/z=615, 609, 558, 399, 213, and 156. The results in FIG. 21 show characteristics derived from [Ir(tBuppm)₂(ppy)] and therefore can be regarded as important data for identifying [Ir(tBuppm)₂(ppy)] contained in a mixture.

It can be presumed that the product ion around m/z=615 is a cation in a state where Hppy is eliminated from [Ir(tBuppm)₂(ppy)]. It can be presumed that the product ion around m/z=558 is a cation in a state where 4-(1,1-dimethylethyl)-6-phenylpyrimidine (abbreviation: HtBuppm) is eliminated from [Ir(tBuppm)₂(ppy)]. It can be presumed that the product ion around m/z=399 is a cation in a state where HtBuppm and Hppy are eliminated from [Ir(tBuppm)₂(ppy)]. It can be presumed that the product ion around m/z=213 is a cation in a state where a proton is added to HtBuppm. It can be presumed that the product ion around m/z=156 is a cation in a state where a proton is added to Hppy. These suggest that [Ir(tBuppm)₂(ppy)] contains HtBuppm and Hppy.

Example 2 Synthesis Example 2

In this example is described a method for synthesizing the organometallic complex of one embodiment of the present invention, bis{2-[6-(1,1-dimethylethyl)-4-pyrimidinyl-κN³]phenyl-κC}[2-(4-methyl-5-phenyl-2-pyridinyl-phenyl-κC]iridium(III) (abbreviation: [Ir(tBuppm)₂(mdppy)]) which is represented by Structural Formula (102) in Embodiment 1. A structure of [Ir(tBuppm)₂(mdppy)] is shown below.

First, 4.9 g of [Ir(tBuppm)₂Cl]₂ (abbreviation) and 450 mL of dichloromethane were put into a three-neck flask, and the atmosphere in the flask was replaced with nitrogen. A mixed solution of 2.9 g of silver trifluoromethanesulfonate and 78 mL of methanol was dripped into the flask, followed by overnight stirring at room temperature. The obtained mixture was filtered through Celite, and the filtrate was concentrated to give a solid. Then, 2.3 g of 4-methyl-2,5-diphenylpyridine (abbreviation: Hmdppy) and 200 mL of ethanol were added to the solid, and the mixture was refluxed in a nitrogen atmosphere for 31 hours.

The obtained mixture was adsorbed on a filter aid in which Celite, silica, and Celite were stacked in this order, followed by washing with hexane and ethanol. After that, dichloromethane was added, and the obtained solution was concentrated, followed by purification by flash column chromatography using ethyl acetate and hexane in a ratio of 1:5 as a developing solvent.

The obtained solution was concentrated, followed by recrystallization from dichloromethane and methanol to give 1.1 g of the organometallic complex [Ir(tBuppm)₂(mdppy)] as an orange solid (yield: 28%).

By a train sublimation method, 0.75 g of the obtained orange solid was purified under a pressure of 2.8 Pa with an argon flow rate of 5 mL/min at 240° C. After the sublimation purification, an orange solid which was a target substance was obtained in a yield of 85%. The synthesis scheme of the above synthesis method is shown in (b) below.

Analysis results by nuclear magnetic resonance (¹H-NMR) spectroscopy of the target substance (orange solid) obtained by the above-described synthesis method are shown below. FIG. 22 shows the ¹H-NMR chart. These results reveal that the organometallic complex [Ir(tBuppm)₂(mdppy)] represented by Structural Formula (102) was obtained in this synthesis example.

¹H-NMR δ (CD₂Cl₂): 1.27 (s, 9H), 1.33 (s, 9H), 2.40 (s, 3H), 6.70 (d, 1H), 6.80-6.81 (m, 2H), 6.84-6.87 (m, 3H), 6.90-6.93 (m, 3H), 7.12 (d, 2H), 7.29-7.33 (m, 4H), 7.68 (d, 1H), 7.77-7.80 (m, 5H), 8.22 (d, 2H).

Next, an ultraviolet-visible absorption spectrum (hereinafter, simply referred to as an “absorption spectrum”) of a deoxidized dichloromethane solution of [Ir(tBuppm)₂(mdppy)] and an emission spectrum thereof were measured. The measurement of the absorption spectrum was conducted at room temperature, for which an ultraviolet and visible spectrophotometer (V550 type manufactured by JASCO Corporation) was used and the dichloromethane solution (0.011 mmol/L) was put in a quartz cell. In addition, the measurement of the emission spectrum was conducted at room temperature, for which an absolute PL quantum yield measurement system (C11347-01 manufactured by Hamamatsu Photonics K.K.) was used and the deoxidized dichloromethane solution (0.011 mmol/L) was sealed in a quartz cell under a nitrogen atmosphere in a glove box (LABstar M13 (1250/780) manufactured by Bright Co., Ltd.).

Measurement results of the obtained absorption and emission spectra are shown in FIG. 23, in which the horizontal axis represents wavelength and the vertical axes represent absorption intensity and emission intensity. In FIG. 23, two solid lines are shown; a thin line represents the absorption spectrum, and a thick line represents the emission spectrum. The absorption spectrum in FIG. 23 is the results obtained in such a way that the absorbance measured by putting only dichloromethane in a quartz cell was subtracted from the absorbance measured by putting the dichloromethane solution (0.011 mmol/L) in a quartz cell.

As shown in FIG. 23, the organometallic complex [Ir(tBuppm)₂(mdppy)] has an emission peak at 555 nm, and yellow light emission was observed from the dichloromethane solution.

Next, [Ir(tBuppm)₂(mdppy)] obtained in this example was subjected to a mass spectrometry (MS) analysis by liquid chromatography-mass spectrometry (LC-MS).

In the LC-MS analysis, liquid chromatography (LC) separation was carried out with ACQUITY UPLC manufactured by Waters Corporation, and mass spectrometry (MS) was carried out with Xevo G2 Tof MS manufactured by Waters Corporation. ACQUITY UPLC BEH C8 (2.1×100 mm, 1.7 μm) was used as a column for the LC separation, and the column temperature was set to 40° C. Acetonitrile was used for Mobile Phase A and a 0.1% aqueous solution of formic acid was used for Mobile Phase B. Furthermore, a sample was prepared in such a manner that [Ir(tBuppm)₂(mdppy)] was dissolved in chloroform at a given concentration and the mixture was diluted with acetonitrile. The injection amount was 5.0 μL.

In the MS analysis, ionization was carried out by an electrospray ionization (ESI) method. At this time, the capillary voltage and the sample cone voltage were set to 3.0 kV and 30 V, respectively, and detection was performed in a positive mode. A component with m/z of 860.33 which underwent the ionization under the above-described conditions was collided with an argon gas in a collision cell to dissociate into product ions. Energy (collision energy) for the collision with argon was set to 50 eV. The measurement mass range was set to m/z=100 to 1200. The detection results of the dissociated product ions by time-of-flight (TOF) MS are shown in FIG. 24.

FIG. 24 shows that product ions of [Ir(tBuppm)₂(mdppy)] are mainly detected around m/z=648, 615, 399, and 246. The results in FIG. 24 show characteristics derived from [Ir(tBuppm)₂(mdppy)] and therefore can be regarded as important data for identifying [Ir(tBuppm)₂(mdppy)] contained in a mixture.

It can be presumed that the product ion around m/z=648 is a cation in a state where HtBuppm is eliminated from [Ir(tBuppm)₂(mdppy)]. This suggests that [Ir(tBuppm)₂(mdppy)] contains HtBuppm. It can be presumed that the product ion around m/z=615 is a cation in a state where Hmdppy is eliminated from [Ir(tBuppm)₂(mdppy)]. It can be presumed that the product ion around m/z=246 is a cation of Hmdppy. This suggests that [Ir(tBuppm)₂(mdppy)] contains Hmdppy.

Example 3 Synthesis Example 3

In this example is described a method for synthesizing the organometallic complex of one embodiment of the present invention, [2-(4,5-dimethyl-2-pyridinyl-κN)phenyl-κC]bis[2-(6-phenyl-4-pyrimidinyl-κN³)phenyl-κC]iridium(III) (abbreviation: [Ir(dppm)₂(dmppy)]) which is represented by Structural Formula (114) in Embodiment 1. A structure of [Ir(dppm)₂(dmppy)] is shown below.

Step 1: Synthesis of 5-bromo-4-methyl-2-phenylpyridine

First, 15 g (60 mmol) of 2,5-dibromo-4-methyl-2-phenylpyridine, 7.3 g (60 mmol) of phenylboronic acid, 3.0 g (22 mmol) of potassium carbonate, 380 mL of toluene, and 38 mL of water were put into a 1000 mL three-neck flask. Then, the atmosphere in the flask was replaced with nitrogen, and the mixture was degassed by being stirred while the pressure in the flask was reduced. After that, the atmosphere in the flask was replaced with nitrogen, and 3.5 g (3.0 mmol) of tetrakis(triphenylphosphine)palladium(0) was added to the mixture. The mixture was stirred at 110° C. for 16 hours under a nitrogen stream.

Water was added to the obtained reaction solution, followed by extraction with toluene. After the organic layer was washed with saturated saline, anhydrous magnesium sulfate was added to the organic layer for drying. This mixture was subjected to gravity filtration, and the filtrate was concentrated to give an oily substance. The obtained oily substance was purified by silica column chromatography. As the developing solvent, a 12:1 hexane-ethyl acetate mixed solvent was used. A fraction of the obtained substance was concentrated to give 13 g of a colorless oily substance. The obtained oily substance was a mixture of a target substance and the source material, 2,5-dibromo-4-methyl-2-phenylpyridine. Therefore, the reaction was repeated two more times to give 6.2 g of the colorless oily target substance in a yield of 42%. The obtained colorless oily substance was identified as 5-bromo-4-methyl-2-phenylpyridine by nuclear magnetic resonance (NMR) spectroscopy. The synthesis scheme of Step 1 is shown in (c-1) below.

Step 2: Synthesis of 4,5-dimethyl-2-phenylpyridine (abbreviation: Hdmppy)

Next, 6.2 g (25 mmol) of 5-bromo-4-methyl-2-phenylpyridine synthesized in Step 1, 5.2 g (41 mmol) of trimethylboroxine, 1.0 g (2.5 mmol) of 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (S-phos), 8.0 g (38 mmol) of tripotassium phosphate, 180 mL of toluene, and 18 mL of water were put into a 500 mL three-neck flask. Then, the atmosphere in the flask was replaced with nitrogen, and the mixture was degassed by being stirred while the pressure in the flask was reduced. After that, the atmosphere in the flask was replaced with nitrogen, and 0.46 g (0.5 mmol) of tris(dibenzylideneacetone)dipalladium(0) was added to the mixture. The mixture was stirred at 110° C. for 23 hours under a nitrogen stream. Water was added to the obtained reaction solution, followed by extraction with toluene. After the organic layer was washed with saturated saline, anhydrous magnesium sulfate was added to the organic layer for drying. This mixture was subjected to gravity filtration, and the filtrate was concentrated to give an oily substance.

The obtained oily substance was purified by silica column chromatography. As the developing solvent, a 20:1 hexane-ethyl acetate mixed solvent was used. A fraction of the obtained substance was concentrated to give 4.5 g of a yellow oily substance in a yield of 98%. The obtained yellow oily substance was identified as 4,5-dimethyl-2-phenylpyridine (abbreviation: Hdmppy) by nuclear magnetic resonance (NMR) spectroscopy. The synthesis scheme of Step 2 is shown in (c-2) below.

Step 3: Synthesis of [2-(4,5-dimethyl-2-pyridinyl-κN²)phenyl-κC]bis[2-(6-phenyl-4-pyrimidinyl-κN³)phenyl-κC]iridium(III) (abbreviation: [Ir(dppm)₂(dmppy)])

Next, 2.1 g (1.5 mmol) of di-μ-chloro-tetrakis[2-(6-phenyl-4-pyrimidinyl-κN³)phenyl-κC]diiridium(III) (abbreviation: [Ir(dppm)₂Cl]₂) and 300 mL of dichloromethane were put into a 1000 mL three-neck flask and stirred under a nitrogen stream. To this mixed solution was dripped a mixed solution of 1.2 g (4.5 mmol) of silver trifluoromethanesulfonate and 150 mL of methanol, and the mixed solution was stirred for 16 hours in a dark place. After the reaction for the predetermined time, the reaction mixture was filtered through Celite.

The obtained filtrate was concentrated to give 2.8 g of a reddish brown solid. Then, 2.8 g of the obtained solid, 30 mL of ethanol, 30 mL of methanol, and 1.1 g (6.0 mmol) of 4,5-dimethyl-2-phenylpyridine (abbreviation: Hdmppy) synthesized in Step 2 were put into a 500 mL recovery flask and were heated and refluxed under a nitrogen stream for 32 hours. After the reaction for the predetermined time, the reaction mixture was concentrated to give a solid. Dichloromethane was added to the obtained solid, and the mixture was filtered through a filter aid in which Celite, neutral silica gel, and Celite were stacked in this order. The obtained filtrate was concentrated, and the obtained oily substance was purified by silica column chromatography. As the developing solvent, first, a 2:1 hexane-dichloromethane mixed solvent was used, and the proportion of dichloromethane was gradually increased. A fraction obtained when the proportion of dichloromethane was 100% was concentrated to give a solid. The obtained solid was recrystallized from ethyl acetate/hexane to give 0.35 g of a red solid in a yield of 14%. The synthesis scheme of Step 3 is shown in (c-3) below.

Analysis results by nuclear magnetic resonance (NMR) spectroscopy of the red solid obtained in Step 3 are shown below. FIG. 25 shows the ¹H-NMR chart. These results reveal that the organometallic complex [Ir(dppm)₂(dmppy)] represented by Structural Formula (114) was obtained in this synthesis example.

¹H-NMR δ (CDCl₃): 2.04 (s, 3H), 2.34 (s, 3H), 6.78 (d, 1H), 6.85 (t, 2H), 6.90-7.01 (m, 6H), 7.44 (s, 1H), 7.48-7.54 (m, 6H), 7.65 (d, 1H), 7.69 (s, 1H), 7.85 (d, 1H), 7.90 (d, 1H), 8.04 (d, 2H), 8.08 (d, 2H), 8.15 (s, 1H), 8.21 (s, 1H), 8.26 (s, 1H), 8.41 (s, 1H).

Next, an ultraviolet-visible absorption spectrum (hereinafter, simply referred to as an “absorption spectrum”) of a dichloromethane solution of [Ir(dppm)₂(dmppy)] and an emission spectrum thereof were measured. The measurement of the absorption spectrum was conducted at room temperature, for which an ultraviolet and visible spectrophotometer (V550 type manufactured by JASCO Corporation) was used and the dichloromethane solution (0.0109 mmol/L) was put in a quartz cell. In addition, the measurement of the emission spectrum was conducted at room temperature, for which an absolute PL quantum yield measurement system (C11347-01 manufactured by Hamamatsu Photonics K.K.) was used and the deoxidized dichloromethane solution (0.0109 mmol/L) was sealed in a quartz cell under a nitrogen atmosphere in a glove box (LABstar M13 (1250/780) manufactured by Bright Co., Ltd.).

Measurement results of the obtained absorption and emission spectra are shown in FIG. 26, in which the horizontal axis represents wavelength and the vertical axes represent absorption intensity and emission intensity. In FIG. 26, two solid lines are shown; a thin line represents the absorption spectrum, and a thick line represents the emission spectrum. The absorption spectrum in FIG. 26 is the results obtained in such a way that the absorbance measured by putting only dichloromethane in a quartz cell was subtracted from the absorbance measured by putting the dichloromethane solution (0.0109 mmol/L) in a quartz cell.

As shown in FIG. 26, the organometallic complex [Ir(dppm)₂(dmppy)] has an emission peak at 613 nm, and orange light emission was observed from the dichloromethane solution.

Next, [Ir(dppm)₂(dmppy)] obtained in this example was subjected to a mass spectrometry (MS) analysis by liquid chromatography-mass spectrometry (LC-MS).

In the LC-MS analysis, liquid chromatography (LC) separation was carried out with ACQUITY UPLC manufactured by Waters Corporation, and mass spectrometry (MS) was carried out with Xevo G2 Tof MS manufactured by Waters Corporation. ACQUITY UPLC BEH C8 (2.1×100 mm, 1.7 μm) was used as a column for the LC separation, and the column temperature was set to 40° C. Acetonitrile was used for Mobile Phase A and a 0.1% aqueous solution of formic acid was used for Mobile Phase B. Furthermore, a sample was prepared in such a manner that [Ir(dppm)₂(dmppy)] was dissolved in chloroform at a given concentration and the mixture was diluted with acetonitrile. The injection amount was 5.0 μL.

In the MS analysis, ionization was carried out by an electrospray ionization (ESI) method. At this time, the capillary voltage and the sample cone voltage were set to 3.0 kV and 30 V, respectively, and detection was performed in a positive mode. A component with m/z of 838.25 which underwent the ionization under the above-described conditions was collided with an argon gas in a collision cell to dissociate into product ions. Energy (collision energy) for the collision with argon was set to 50 eV. The measurement mass range was set to m/z=100 to 1200. The detection results of the dissociated product ions by time-of-flight (TOF) MS are shown in FIG. 27.

FIG. 27 shows that product ions of [Ir(dppm)₂(dmppy)] are mainly detected around m/z=653, 604, 423, 233, and 184. The results in FIG. 27 show characteristics derived from [Ir(dppm)₂(dmppy)] and therefore can be regarded as important data for identifying [Ir(dppm)₂(dmppy)] contained in a mixture.

It can be presumed that the product ion around m/z=653 is a cation in a state where Hdmppy is eliminated from [Ir(dppm)₂(dmppy)]. It can be presumed that the product ion around m/z=604 is a cation in a state where 4,6-diphenylpyrimidine (abbreviation: Hdppm) is eliminated from [Ir(dppm)₂(dmppy)]. It can be presumed that the product ion around m/z=423 is a cation in a state where Hdppm and Hdmppy are eliminated from [Ir(dppm)₂(dmppy)]. It can be presumed that the product ion around m/z=233 is a cation in a state where a proton is added to Hdppm. It can be presumed that the product ion around m/z=184 is a cation in a state where a proton is added to Hdmppy. These suggest that [Ir(dppm)₂(dmppy)] contains Hdppm and Hdmppy.

Example 4 Synthesis Example 4

In this example is described a method for synthesizing the organometallic complex of one embodiment of the present invention, {2-[6-(1,1-dimethylethyl)-4-pyrimidinyl-κN³]phenyl-κC}bis[2-(4-methyl-5-phenyl-2-pyridinyl-κN)phenyl-κC]iridium(III) (abbreviation: [Ir(tBuppm)(mdppy)₂]) which is represented by Structural Formula (120) in Embodiment 1. A structure of [Ir(tBuppm)(mdppy)₂] is shown below.

Step 1: Synthesis of di-μ-chloro-tetrakis[2-(4-methyl-5-phenyl-2-pyridinyl-κN)phenyl-κC]diiridium(III) (abbreviation: [Ir(mdppy)₂Cl]₂)

First, 3.0 g of 4-methyl-2,5-diphenylpyridine (abbreviation: Hmdppy), 1.8 g of iridium(III) chloride hydrate, 30 mL of 2-ethoxyethanol, and 10 mL of water were put into a round-bottom flask with a reflux pipe and irradiated with microwaves (2.45 GHz, 100 W) for 2 hours while being bubbled with argon. The obtained mixture was filtered, followed by washing with methanol and hexane to give 2.9 g of a target substance (a dark yellow solid in a yield of 65%). The synthesis scheme of Step 1 is shown in (d-1) below.

Step 2: Synthesis of {2-[6-(1,1-dimethylethyl)-4-pyrimidinyl-κN³]phenyl-κC}bis[2-(4-methyl-5-phenyl-2-pyridinyl-κN)phenyl-κC]iridium(III) (abbreviation: [Ir(tBuppm)(mdppy)₂])

Next, 2.9 g of [Ir(mdppy)₂Cl]₂ and 430 mL of dichloromethane were put into a three-neck flask, and the atmosphere in the flask was replaced with nitrogen. A mixed solution of 1.0 g of silver triflate and 53 mL of 2-propanol was dripped into the flask, followed by stirring at room temperature for 18 hours. The obtained mixture was filtered through Celite, and the filtrate was concentrated to give a solid. Then, 2.3 g of HtBuppm (abbreviation) and 40 mL of ethanol were added to the solid, and the mixture was refluxed in a nitrogen atmosphere for 18 hours. The obtained mixture was filtered, and the residue was purified by silica column chromatography using ethyl acetate and hexane in a ratio of 1:5 as a developing solvent. During the purification, the proportion of hexane was gradually decreased, and the ratio of ethyl acetate to hexane was 1:2 at the end. Further purification was performed by flash column chromatography using dichloromethane and hexane in a ratio of 1:2 as a developing solvent. The obtained solution was concentrated, followed by recrystallization from dichloromethane and hexane to give the organometallic complex [Ir(tBuppm)(mdppy)₂] as an orange solid (yield: 29%).

By a train sublimation method, 0.90 g of the obtained orange solid was purified under a pressure of 2.7 Pa with an argon flow rate of 5 mL/min at 260° C. After the sublimation purification, an orange solid which was a target substance was obtained in a yield of 88%. The synthesis scheme of Step 2 is shown in (d-2) below.

Analysis results by nuclear magnetic resonance (¹H-NMR) spectroscopy of the target substance (orange solid) obtained in Step 2 are shown below. FIG. 28 shows the ¹H-NMR chart. These results reveal that the organometallic complex [Ir(tBuppm)(mdppy)₂] represented by Structural Formula (120) was obtained in this synthesis example.

¹H-NMR δ (CDCl₃): 1.30 (s, 9H), 2.32 (s, 3H), 2.37 (s, 3H), 6.83-6.97 (m, 9H), 6.99-7.01 (m, 2H), 7.13 (d, 2H), 7.28-7.36 (m, 7H), 7.45 (s, 1H), 7.64-7.68 (m, 2H), 7.70 (s, 1H), 7.74 (d, 3H), 8.21 (s, 1H).

Next, an ultraviolet-visible absorption spectrum (hereinafter, simply referred to as an “absorption spectrum”) of a deoxidized dichloromethane solution of [Ir(tBuppm)(mdppy)₂] and an emission spectrum thereof were measured. The measurement of the absorption spectrum was conducted at room temperature, for which an ultraviolet and visible spectrophotometer (V550 type manufactured by JASCO Corporation) was used and the dichloromethane solution (0.011 mmol/L) was put in a quartz cell. In addition, the measurement of the emission spectrum was conducted at room temperature, for which an absolute PL quantum yield measurement system (C11347-01 manufactured by Hamamatsu Photonics K.K.) was used and the deoxidized dichloromethane solution (0.011 mmol/L) was sealed in a quartz cell under a nitrogen atmosphere in a glove box (LABstar M13 (1250/780) manufactured by Bright Co., Ltd.).

Measurement results of the obtained absorption and emission spectra are shown in FIG. 29, in which the horizontal axis represents wavelength and the vertical axes represent absorption intensity and emission intensity. In FIG. 29, two solid lines are shown; a thin line represents the absorption spectrum, and a thick line represents the emission spectrum. The absorption spectrum in FIG. 29 is the results obtained in such a way that the absorbance measured by putting only dichloromethane in a quartz cell was subtracted from the absorbance measured by putting the dichloromethane solution (0.011 mmol/L) in a quartz cell.

As shown in FIG. 29, the organometallic complex [Ir(tBuppm)(mdppy)₂] has an emission peak at 572 nm, and orange light emission was observed from the dichloromethane solution.

Next, [Ir(tBuppm)(mdppy)₂] obtained in this example was subjected to a mass spectrometry (MS) analysis by liquid chromatography-mass spectrometry (LC-MS).

In the LC-MS analysis, liquid chromatography (LC) separation was carried out with ACQUITY UPLC (registered trademark) manufactured by Waters Corporation, and mass spectrometry (MS) was carried out with Xevo G2 Tof MS manufactured by Waters Corporation. ACQUITY UPLC BEH C8 (2.1×100 mm, 1.7 μm) was used as a column for the LC separation, and the column temperature was set to 40° C. Acetonitrile was used for Mobile Phase A and a 0.1% aqueous solution of formic acid was used for Mobile Phase B. Furthermore, a sample was prepared in such a manner that [Ir(tBuppm)(mdppy)₂] was dissolved in chloroform at a given concentration and the mixture was diluted with acetonitrile. The injection amount was 5.0 μL.

In the MS analysis, ionization was carried out by an electrospray ionization (ESI) method. At this time, the capillary voltage and the sample cone voltage were set to 3.0 kV and 30 V, respectively, and detection was performed in a positive mode. A component with m/z of 893.32 which underwent the ionization under the above-described conditions was collided with an argon gas in a collision cell to dissociate into product ions. Energy (collision energy) for the collision with argon was set to 70 eV. The measurement mass range was set to m/z=100 to 1200. The detection results of the dissociated product ions by time-of-flight (TOF) MS are shown in FIG. 30.

FIG. 30 shows that product ions of [Ir(tBuppm)(mdppy)₂] are mainly detected around m/z=681, 648, 640, 632, 618, 510, 399, 387, and 246. The results in FIG. 30 show characteristics derived from [Ir(tBuppm)(mdppy)₂] and therefore can be regarded as important data for identifying [Ir(tBuppm)(mdppy)₂] contained in a mixture.

It can be presumed that the product ion around m/z=681 is a cation in a state where HtBuppm (abbreviation) is eliminated from [Ir(tBuppm)(mdppy)₂]. This suggests that [Ir(tBuppm)(mdppy)₂] contains HtBuppm.

It can be presumed that the product ion around m/z=648 is a cation in a state where 4-methyl-2,5-diphenylpyridine (abbreviation: Hmdppy) is eliminated from [Ir(tBuppm)(mdppy)₂]. It can be presumed that the product ion around m/z=399 is a cation derived from a state where two Hmdppy ligands are eliminated from [Ir(tBuppm)(mdppy)₂]. This suggests that [Ir(tBuppm)(mdppy)₂] contains two Hmdppy ligands.

It can be presumed that the product ion around m/z=632 is a cation derived from a state where a methyl group is eliminated from the product ion around m/z=648. It can be presumed that the product ion around m/z=618 is a cation derived from a state where a methyl group is further eliminated from the product ion around m/z=632. It can be presumed that the product ion around m/z=387 is a cation derived from a state where a methyl group is eliminated from the product ion around m/z=399. It can be presumed that the product ion around m/z=246 is a cation of Hmdppy in [Ir(tBuppm)(mdppy)₂]. This suggests that [Ir(tBuppm)(mdppy)₂] contains Hmdppy.

Example 5

In this example, a light-emitting element 1 including [Ir(tBuppm)₂(mdppy)] (Structural Formula (102)) which is the organometallic complex of one embodiment of the present invention, a light-emitting element 2 including [Ir(tBuppm)(mdppy)₂] (Structural Formula (120)), a comparative light-emitting element 3 including [Ir(tBuppm)₃] (Structural Formula (500)), and a comparative light-emitting element 4 including [Ir(mdppy)₃] (Structural Formula (600)) were fabricated. Note that the fabrication of these light-emitting elements is described with reference to FIG. 31. Chemical formulae of materials used in this example are shown below.

<<Fabrication of Light-Emitting Elements>>

First, indium tin oxide (ITO) containing silicon oxide was deposited over a glass substrate 900 by a sputtering method, whereby a first electrode 901 functioning as an anode was formed. Note that the thickness was set to 110 nm and the electrode area was set to 2 mm×2 mm.

Next, as pretreatment for forming the light-emitting element over the substrate 900, UV ozone treatment was performed for 370 seconds after washing of a surface of the substrate with water and after baking at 200° C. for 1 hour.

After that, the substrate was transferred into a vacuum evaporation apparatus where the pressure had been reduced to approximately 1×10⁻⁴ Pa, and was subjected to vacuum baking at 170° C. for 30 minutes in a heating chamber of the vacuum evaporation apparatus. Then, the substrate 900 was cooled down for approximately 30 minutes.

Next, the substrate 900 was fixed to a holder provided in the vacuum evaporation apparatus so that a surface of the substrate over which the first electrode 901 was formed faced downward. In this example, a case is described in which a hole-injection layer 911, a hole-transport layer 912, a light-emitting layer 913, an electron-transport layer 914, and an electron-injection layer 915, which are included in an EL layer 902, are sequentially formed by a vacuum evaporation method.

After reducing the pressure in the vacuum evaporation apparatus to 1×10⁻⁴ Pa, 1,3,5-tri(dibenzothiophen-4-yl)benzene (abbreviation: DBT3P-II) and molybdenum oxide were deposited by co-evaporation with a mass ratio of DBT3P-II to molybdenum oxide being 4:2, whereby the hole-injection layer 911 was formed over the first electrode 901. The thickness of the hole-injection layer 911 was set to 60 nm. Note that co-evaporation is an evaporation method in which a plurality of different substances are concurrently vaporized from different evaporation sources.

Then, 4-phenyl-4′-(9-phenylfluoren-9-yl)triphenylamine (abbreviation: BPAFLP) was deposited by evaporation to a thickness of 20 nm, whereby the hole-transport layer 912 was formed.

Next, the light-emitting layer 913 was formed over the hole-transport layer 912.

For fabrication of the light-emitting element 1, 2-[3′-(dibenzothiophen-4-yl)biphenyl-3-yl]dibenzo[f,h]quinoxaline (abbreviation: 2mDBTBPDBq-II), N-(1,1′-biphenyl-4-yl)-9,9-dimethyl-N-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-9H-fluoren-2-amine (abbreviation: PCBBiF), and [Ir(tBuppm)₂(mdppy)] were deposited by co-evaporation to a thickness of 20 nm with a mass ratio of 2mDBTBPDBq-II to PCBBiF to [Ir(tBuppm)₂(mdppy)] being 0.7:0.3:0.075. Furthermore, 2mDBTBPDBq-II, PCBBiF, and [Ir(tBuppm)₂(mdppy)] were deposited by co-evaporation to a thickness of 20 nm with a mass ratio of 2mDBTBPDBq-II to PCBBiF to [Ir(tBuppm)₂(mdppy)] being 0.8:0.2:0.075. Through the above process, the light-emitting layer 913 of the light-emitting element 1 was formed to a thickness of 40 nm.

For fabrication of the light-emitting element 2, 2mDBTBPDBq-II, PCBBiF, and [Ir(tBuppm)(mdppy)₂] were deposited by co-evaporation to a thickness of 20 nm with a mass ratio of 2mDBTBPDBq-II to PCBBiF to [Ir(tBuppm)(mdppy)₂] being 0.7:0.3:0.075. Furthermore, 2mDBTBPDBq-II, PCBBiF, and [Ir(tBuppm)₂(mdppy)] were deposited by co-evaporation to a thickness of 20 nm with a mass ratio of 2mDBTBPDBq-II to PCBBiF to [Ir(tBuppm)₂(mdppy)] being 0.8:0.2:0.075. Through the above process, the light-emitting layer 913 of the light-emitting element 2 was formed to a thickness of 40 nm.

For fabrication of the comparative light-emitting element 3, 2mDBTBPDBq-II, PCBBiF, and [Ir(tBuppm)₃] were deposited by co-evaporation to a thickness of 20 nm with a mass ratio of 2mDBTBPDBq-II to PCBBiF to [Ir(tBuppm)₃] being 0.7:0.3:0.075. Furthermore, 2mDBTBPDBq-II, PCBBiF, and [Ir(tBuppm)₃] were deposited by co-evaporation to a thickness of 20 nm with a mass ratio of 2mDBTBPDBq-II to PCBBiF to [Ir(tBuppm)₃] being 0.8:0.2:0.075. Through the above process, the light-emitting layer 913 of the comparative light-emitting element 3 was formed to a thickness of 40 nm.

For fabrication of the comparative light-emitting element 4, 2mDBTBPDBq-II, PCBBiF, and [Ir(mdppy)₃] were deposited by co-evaporation to a thickness of 20 nm with a mass ratio of 2mDBTBPDBq-II to PCBBiF to [Ir(mdppy)₃] being 0.7:0.3:0.075. Furthermore, 2mDBTBPDBq-II, PCBBiF, and [Ir(mdppy)₃] were deposited by co-evaporation to a thickness of 20 nm with a mass ratio of 2mDBTBPDBq-II to PCBBiF to [Ir(mdppy)₃] being 0.8:0.2:0.075. Through the above process, the light-emitting layer 913 of the comparative light-emitting element 4 was formed to a thickness of 40 nm.

Next, over the light-emitting layer 913 of each of these light-emitting elements, 2mDBTBPDBq-II was deposited by evaporation to a thickness of 20 nm, and then BPhen was deposited by evaporation to a thickness of 10 nm, whereby the electron-transport layer 914 was formed.

Furthermore, lithium fluoride was deposited by evaporation to a thickness of 1 nm over the electron-transport layer 914, whereby the electron-injection layer 915 was formed.

Finally, aluminum was deposited by evaporation to a thickness of 200 nm over the electron-injection layer 915, whereby a second electrode 903 functioning as a cathode was formed. Thus, each of the light-emitting elements was obtained. Note that in all the above evaporation steps, evaporation was performed by a resistance-heating method.

Table 1 shows the element structures of the light-emitting elements fabricated by the above-described method.

TABLE 1 Hole- Hole- Light- Electron- First injection transport emitting injection Second electrode layer layer layer Electron-transport layer layer electrode Light-emitting ITO DBT3P-II: BPAFLP * 2mDBTBPDBq-II BPhen LiF Al element 1 (70 nm) MoOx (20 nm) (20 nm) (10 nm) (1 nm) (200 nm) (4:2, 60 nm) Light-emitting ITO DBT3P-II: BPAFLP ** 2mDBTBPDBq-II BPhen LiF Al element 2 (70 nm) MoOx (20 nm) (20 nm) (10 nm) (1 nm) (200 nm) (4:2, 60 nm) Comparative ITO DBT3P-II: BPAFLP *** 2mDBTBPDBq-II BPhen LiF Al light-emitting (70 nm) MoOx (20 nm) (20 nm) (10 nm) (1 nm) (200 nm) element 3 (4:2, 60 nm) Comparative ITO DBT3P-II: BPAFLP **** 2mDBTBPDBq-II BPhen LiF Al light-emitting (70 nm) MoOx (20 nm) (20 nm) (10 nm) (1 nm) (200 nm) element 4 (4:2, 60 nm) *2mDBTBPDBq-II:PCBBiF:[Ir(tBuppm)₂(mdppy)] (0.7:0.3:0.075 (20 nm)\0.8:0.2:0.075 (20 nm)) **2mDBTBPDBq-II:PCBBiF:[Ir(tBuppm)(mdppy)₂] (0.7:0.3:0.075 (20 nm)\0.8:0.2:0.075 (20 nm)) ***2mDBTBPDBq-II:PCBBiF:[Ir(tBuppm)₃] (0.7:0.3:0.075 (20 nm)\0.8:0.2:0.075 (20 nm)) ****2mDBTBPDBq-II:PCBBiF:[Ir(mdppy)₃] (0.7:0.3:0.075 (20 nm)\0.8:0.2:0.075 (20 nm))

The fabricated light-emitting elements were each sealed in a glove box containing a nitrogen atmosphere so as not to be exposed to the air (specifically, a sealant was applied to surround the elements, and at the time of sealing, UV treatment was performed first and then heat treatment was performed at 80° C. for 1 hour).

<<Operation Characteristics of Light-Emitting Elements>>

Operation characteristics of the light-emitting elements were measured. Note that the measurement was carried out at room temperature (in an atmosphere where a temperature was maintained at 25° C.).

FIG. 32, FIG. 33, FIG. 34, and FIG. 35 show current density-luminance characteristics, voltage-luminance characteristics, luminance-current efficiency characteristics, and voltage-current characteristics, respectively, of the light-emitting element 1, the light-emitting element 2, the comparative light-emitting element 3, and the comparative light-emitting element 4.

Table 2 shows initial values of main characteristics of the light-emitting elements at around 1000 cd/m².

TABLE 2 Current Current Power External Voltage Current density Chromaticity Luminance efficieincy efficiency quantum (V) (mA) (mA/cm²) (x, y) (cd/m²) (cd/A) (1 m/W) efficiency (%) Light-emitting 2.7 0.047 1.2 (0.42, 0.57) 1000  89 100 24 element 1 Light-emitting 2.8 0.053 1.3 (0.47, 0.53) 840 63  71 19 element 2 Comparative 2.7 0.042 1.0 (0.38, 0.60) 980 94 110 26 light-emitting element 3 Comparative 2.6 0.044 1.1 (0.36, 0.62) 790 71  86 19 light-emitting element 4

FIG. 36 shows emission spectra of the light-emitting element 1, the light-emitting element 2, the comparative light-emitting element 3, and the comparative light-emitting element 4 to which current was applied at a current density of 2.5 mA/cm². The emission spectrum of the light-emitting element 1 derives from [Ir(tBuppm)₂(mdppy)] and has a peak at around 545 nm. The emission spectrum of the light-emitting element 2 derives from [Ir(tBuppm)(mdppy)₂] and has a peak at around 556 nm. The emission spectrum of the comparative light-emitting element 3 derives from [Ir(tBuppm)₃] and has a peak at around 536 nm. The emission spectrum of the comparative light-emitting element 4 derives from [Ir(mdppy)₃] and has a peak at around 530 nm.

Next, reliability tests were performed on the light-emitting elements. FIG. 37 shows results of the reliability tests. In FIG. 37, the vertical axis represents normalized luminance (%) with an initial luminance of 100%, and the horizontal axis represents driving time (h) of the elements. As the reliability tests, driving tests at a constant current of 2 mA were performed.

The results shown in FIG. 37 reveal that each of the light-emitting elements 1 and 2 including the organometallic complex of one embodiment of the present invention has higher reliability than the comparative light-emitting element 3 or 4. A probable reason for this is that the organometallic complex of one embodiment of the present invention has a shallow HOMO and a deep LUMO as a whole because the HOMO and the LUMO are spatially separated from each other by being distributed over different ligands. In other words, in each of the organometallic complexes used as the light-emitting materials in the light-emitting elements 1 and 2, both at the time of carrier transport and in an excited state, holes are distributed over a ligand that is highly resistant to holes (the first ligand over which the HOMO is likely to be distributed), and electrons are distributed over a ligand that is highly resistant to electrons (the second ligand over which the LUMO is likely to be distributed). This probably makes it possible to increase stability at the time of carrier transport and in an excited state and to manufacture a light-emitting element with long lifetime. Furthermore, by such separation of the HOMO and the LUMO from each other, the organometallic complex itself can transport both carriers; thus, carrier balance can be adjusted and a recombination region in the light-emitting layer can be prevented from becoming narrow in a light-emitting element manufactured using this organometallic complex. This can also be considered a factor for achieving an increase of lifetime.

Note that the compound (500) used in the comparative light-emitting element 3 includes three tBuppm ligands, and the compound (600) used in the comparative light-emitting element 4 includes three mdppy ligands. However, each of the light-emitting elements 1 and 2 fabricated using the organometallic complex of one embodiment of the present invention, which includes both a tBuppm ligand(s) having a pyrimidine ring and a mdppy ligand(s) having a pyridine ring, has longer lifetime than the comparative light-emitting element 3 or 4. This means that the two kinds of ligands in the organometallic complex of one embodiment of the present invention exhibit a new function of increasing lifetime rather than a mere combination of their functions. This is a surprising phenomenon. Such an effect is probably obtained because the LUMO and the HOMO are distributed over tBuppm that is a pyrimidine ligand and mdppy that is a pyridine ligand, respectively, as described below.

In the light-emitting element 2 fabricated using the organometallic complex with two mdppy ligands and one tBuppm ligand, the effect of increasing lifetime is particularly significant. This indicates that the presence of two ligands over which the HOMO is distributed and one ligand over which the LUMO is distributed is important in terms of an increase in lifetime. That is, an organometallic complex is more stable when including more ligands capable of accepting holes, but has shorter lifetime when including only ligands capable of accepting holes.

Example 6

In this example, a light-emitting element 5 including [Ir(tBuppm)₂(ppy)] (Structural Formula (100)) which is the organometallic complex of one embodiment of the present invention was fabricated. Note that the fabrication of the light-emitting element 5 is described with reference to FIG. 31 as in Example 5. Chemical formulae of materials used in this example are shown below.

<<Fabrication of Light-Emitting Element>>

First, indium tin oxide (ITO) containing silicon oxide was deposited over a glass substrate 900 by a sputtering method, whereby a first electrode 901 functioning as an anode was formed. Note that the thickness was set to 70 nm and the electrode area was set to 2 mm×2 mm.

Next, as pretreatment for forming the light-emitting element over the substrate 900, UV ozone treatment was performed for 370 seconds after washing of a surface of the substrate with water and after baking at 200° C. for 1 hour.

After that, the substrate was transferred into a vacuum evaporation apparatus where the pressure had been reduced to approximately 1×10⁻⁴ Pa, and was subjected to vacuum baking at 170° C. for 30 minutes in a heating chamber of the vacuum evaporation apparatus. Then, the substrate 900 was cooled down for approximately 30 minutes.

Next, the substrate 900 was fixed to a holder provided in the vacuum evaporation apparatus so that a surface of the substrate over which the first electrode 901 was formed faced downward. In this example, a case is described in which a hole-injection layer 911, a hole-transport layer 912, a light-emitting layer 913, an electron-transport layer 914, and an electron-injection layer 915, which are included in an EL layer 902, are sequentially formed by a vacuum evaporation method.

After reducing the pressure in the vacuum evaporation apparatus to 1×10⁻⁴ Pa, 1,3,5-tri(dibenzothiophen-4-yl)benzene (abbreviation: DBT3P-II) and molybdenum oxide were deposited by co-evaporation with a mass ratio of DBT3P-II to molybdenum oxide being 4:2, whereby the hole-injection layer 911 was formed over the first electrode 901. The thickness of the hole-injection layer 911 was set to 60 nm. Note that co-evaporation is an evaporation method in which a plurality of different substances are concurrently vaporized from different evaporation sources.

Then, 9-phenyl-9H-3-(9-phenyl-9H-carbazol-3-yl)carbazole (abbreviation: PCCP) was deposited by evaporation to a thickness of 20 nm, whereby the hole-transport layer 912 was formed.

Next, the light-emitting layer 913 was formed over the hole-transport layer 912.

For fabrication of the light-emitting element 5, 2-[3′-(dibenzothiophen-4-yl)biphenyl-3-yl]dibenzo[f,h]quinoxaline (abbreviation: 2mDBTBPDBq-II), N-(1,1′-biphenyl-4-yl)-9,9-dimethyl-N-[4-(9-phenyl-9H-carbazol-3-yl)phenyl]-9H-fluoren-2-amine (abbreviation: PCBBiF), and [Ir(tBuppm)₂(ppy)] (Structural Formula (100)) were deposited by co-evaporation to a thickness of 40 nm with a mass ratio of 2mDBTBPDBq-II to PCBBiF to [Ir(tBuppm)₂(ppy)] being 0.8:0.2:0.05. Through the above process, the light-emitting layer 913 of the light-emitting element 5 was formed to a thickness of 40 nm.

Next, over the light-emitting layer 913, 2mDBTBPDBq-II was deposited by evaporation to a thickness of 20 nm, and then BPhen was deposited by evaporation to a thickness of 10 nm, whereby the electron-transport layer 914 was formed.

Furthermore, lithium fluoride was deposited by evaporation to a thickness of 1 nm over the electron-transport layer 914, whereby the electron-injection layer 915 was formed.

Finally, aluminum was deposited by evaporation to a thickness of 200 nm over the electron-injection layer 915, whereby a second electrode 903 functioning as a cathode was formed. Thus, the light-emitting element was obtained. Note that in all the above evaporation steps, evaporation was performed by a resistance-heating method.

Table 3 shows the element structure of the light-emitting element 5 fabricated by the above-described method.

TABLE 3 Hole- Hole- Light- Electron- First injection transport emitting injection Second electrode layer layer layer Electron-transport layer layer electrode Light-emitting ITO DBT3P-II: BPAFLP * 2mDBTBPDBq-II BPhen LiF Al element 5 (70 nm) MoOx (20 nm) (20 nm) (10 nm) (1 nm) (200 nm) (4:2, 20 nm) *2mDBTBPDBq-II:PCBBiF:[Ir(tBuppm)₂(ppy)] (0.8:0.2:0.05 (40 nm))

The fabricated light-emitting element was sealed in a glove box containing a nitrogen atmosphere so as not to be exposed to the air (specifically, a sealant was applied to surround the element, and at the time of sealing, UV treatment was performed first and then heat treatment was performed at 80° C. for 1 hour).

<<Operation Characteristics of Light-Emitting Element>>

Operation characteristics of the light-emitting element 5 were measured. Note that the measurement was carried out at room temperature (in an atmosphere where a temperature was maintained at 25° C.).

FIG. 38, FIG. 39, FIG. 40, and FIG. 41 show current density-luminance characteristics, voltage-luminance characteristics, luminance-current efficiency characteristics, and voltage-current characteristics, respectively, of the light-emitting element 5.

Table 4 shows initial values of main characteristics of the light-emitting element 5 at around 1000 cd/m².

TABLE 4 Current Current Power External Voltage Current density Chromaticity Luminance efficieincy efficiency quantum (V) (mA) (mA/cm²) (x, y) (cd/m²) (cd/A) (1 m/W) efficiency (%) Light-emitting 2.8 0.044 1.1 (0.42, 0.57) 940 85 95 23 element 5

FIG. 42 shows an emission spectrum of the light-emitting element 5 to which current was applied at a current density of 2.5 mA/cm². As shown in FIG. 42, the emission spectrum of the light-emitting element 5 has a peak at around 545 nm, which indicates that the emission spectrum derives from green light emission of the organometallic complex [Ir(tBuppm)₂(ppy)] of one embodiment of the present invention.

Example 7

In this example are described results of molecular orbital calculations of organometallic complexes of one embodiment of the present invention, which are represented by Structural Formulae (C1) to (C7). Note that (C1) represents a compound obtained by simply substituting a methyl group for a t-butyl group of the organometallic complex used in the light-emitting element 5. (C2) represents a compound obtained by simply substituting a methyl group for a t-butyl group of the organometallic complex used in the light-emitting element 1. (C6) represents a compound obtained by simply substituting a methyl group for a t-butyl group of the organometallic complex used in the light-emitting element 2. To reduce calculation load, the methyl group is substituted for the t-butyl group of each of the compounds; however, the alkyl length hardly affects HOMO-LUMO distributions. Therefore, these calculation results can be considered to reflect the HOMO-LUMO distributions of the compounds used in the examples.

Note that Gaussian 09 was used for molecular orbital calculations. As a basis function, 6-311G was used, and structural optimization was performed on the singlet ground state (S₀) of each molecule using B3PW91\6-311G.

Table 5 shows calculated electron density distributions of the HOMO and the LUMO of each organometallic complex.

TABLE 5 Structural Formula HOMO LUMO (C1)

(C2)

(C3)

(C4)

(C5)

(C6)

(C7)

As the results in Table 5 show, the HOMO of the organometallic complex represented by Structural Formula (C1) is mainly distributed over a phenylpyridine ligand and an iridium ion, and the LUMO thereof is mainly distributed over a ligand of a phenylpyrimidine derivative. The HOMO of the organometallic complex represented by Structural Formula (C2) is mainly distributed over a ligand of a phenylpyridine derivative and an iridium ion, and the LUMO thereof is mainly distributed over a ligand of a phenylpyrimidine derivative. The HOMO of the organometallic complex represented by Structural Formula (C3) is mainly distributed over a phenylpyridine ligand and an iridium ion, and the LUMO thereof is mainly distributed over a ligand of a phenylpyrimidine derivative. The HOMO of each of the organometallic complexes represented by Structural Formulae (C4) and (C5) is mainly distributed over a phenylpyridine ligand and an iridium ion, and the LUMO thereof is mainly distributed over a ligand of a phenyltriazine derivative.

The HOMO of the iridium complex represented by Structural Formula (C6) is mainly distributed over a ligand of a phenylpyridine derivative and an iridium ion, and the LUMO thereof is mainly distributed over a ligand of a phenylpyrimidine derivative. The HOMO of the iridium complex represented by Structural Formula (C7) is mainly distributed over a phenylpyridine ligand and an iridium ion, and the LUMO thereof is mainly distributed over a ligand of a phenylpyrimidine derivative.

As described above, an organometallic complex whose HOMO and LUMO are mainly distributed over different ligands when the organometallic complex is subjected to structural optimization by molecular orbital calculation using B3PW91 as a functional and 6-311G as a basis function can be used as the organometallic complex of one embodiment of the present invention. Such a structure can be obtained by an appropriate combination of a ligand which makes the HOMO shallow and a ligand which makes the LUMO deep, as described in the above example. The resulting organometallic complex of one embodiment of the present invention has high resistance to both electrons and holes and high resistance to excited states and can therefore improve the lifetime of an element when used as a light-emitting material of the element. In addition, owing to its excellent carrier-injection and carrier-transport properties with respect to both electrons and holes, a light-emitting element with low drive voltage and high emission efficiency can be obtained. Furthermore, owing to the excellent carrier-injection and carrier-transport properties, carrier balance can be adjusted, which contributes to an increase of lifetime.

Example 8 Synthesis Example 5

In this example is described a method for synthesizing the organometallic complex of one embodiment of the present invention, bis{2-[6-(1,1-dimethylethyl)-4-pyrimidinyl-κN³]phenyl-κC}[2-(4-phenyl-2-pyridinyl-κN)phenyl-κC]iridium(III) (abbreviation: [Ir(tBuppm)₂(4dppy)]) which is represented by Structural Formula (117) in Embodiment 1. A structure of [Ir(tBuppm)₂(4dppy)] is shown below.

First, 3.6 g of [Ir(tBuppm)₂Cl]₂ (abbreviation) and 250 mL of dichloromethane were put into a three-neck flask, and the atmosphere in the flask was replaced with nitrogen. A mixed solution of 2.1 g of silver trifluoromethanesulfonate and 30 mL of methanol was dripped into the flask, followed by stirring at room temperature for 20 hours.

The obtained mixture was filtered through Celite. The obtained filtrate was concentrated to give a solid. Then, 3.1 g of 2,4-diphenylpyridine (abbreviation: H4dppy) and 100 mL of ethanol were added to the solid, and the mixture was heated and refluxed in a nitrogen atmosphere for 23 hours.

The obtained reaction product was concentrated to give a solid. The obtained solid was purified by neutral silica gel column chromatography using chloroform and hexane in a ratio of 2:3 as a developing solvent. A fraction of the obtained substance was concentrated, followed by recrystallization from dichloromethane and methanol to give 1.7 g of the organometallic complex [Ir(tBuppm)₂(4dppy)] as an orange solid (yield: 36%).

By a train sublimation method, 1.7 g of the obtained orange solid was purified under a pressure of 3.0 Pa with an argon flow rate of 5 mL/min at 285° C. After the sublimation purification, an orange solid which was a target substance was obtained in a yield of 94%. The synthesis scheme of the above synthesis method is shown in (e) below.

Analysis results by nuclear magnetic resonance (¹H-NMR) spectroscopy of the orange solid obtained by the above-described synthesis method are shown below. FIG. 43 shows the ¹H-NMR chart. These results reveal that the organometallic complex [Ir(tBuppm)₂(4dppy)] represented by Structural Formula (117) was obtained in this synthesis example.

¹H-NMR δ (CD₂Cl₂): 1.36 (s, 9H), 1.39 (s, 9H), 6.82 (d, 1H), 6.85-6.88 (1H), 6.89-6.98 (m, 7H), 7.13 (dd, 1H), 7.44-7.52 (m, 3H), 7.62 (d, 2H), 7.66 (d, 1H), 7.76-7.81 (m, 5H), 8.06 (s, 1H), 8.24 (s, 1H), 8.27 (s, 1H).

Next, an ultraviolet-visible absorption spectrum (hereinafter, simply referred to as an “absorption spectrum”) of a deoxidized dichloromethane solution of [Ir(tBuppm)₂(4dppy)] and an emission spectrum thereof were measured. The measurement of the absorption spectrum was conducted at room temperature, for which an ultraviolet and visible spectrophotometer (V550 type manufactured by JASCO Corporation) was used and the dichloromethane solution (0.013 mmol/L) was put in a quartz cell. In addition, the measurement of the emission spectrum was conducted at room temperature, for which an absolute PL quantum yield measurement system (C11347-01 manufactured by Hamamatsu Photonics K.K.) was used and the deoxidized dichloromethane solution (0.013 mmol/L) was sealed in a quartz cell under a nitrogen atmosphere in a glove box (LABstar M13 (1250/780) manufactured by Bright Co., Ltd.).

Measurement results of the obtained absorption and emission spectra are shown in FIG. 44, in which the horizontal axis represents wavelength and the vertical axes represent absorption intensity and emission intensity. In FIG. 44, two solid lines are shown; a thin line represents the absorption spectrum, and a thick line represents the emission spectrum. The absorption spectrum in FIG. 44 is the results obtained in such a way that the absorbance measured by putting only dichloromethane in a quartz cell was subtracted from the absorbance measured by putting the dichloromethane solution (0.013 mmol/L) in a quartz cell.

As shown in FIG. 44, the organometallic complex [Ir(tBuppm)₂(4dppy)] has an emission peak at 552 nm, and yellow light emission was observed from the dichloromethane solution.

Next, [Ir(tBuppm)₂(4dppy)] obtained in this example was subjected to a mass spectrometry (MS) analysis by liquid chromatography-mass spectrometry (LC-MS).

In the LC-MS analysis, liquid chromatography (LC) separation was carried out with UltiMate 3000 manufactured by Thermo Fisher Scientific K.K., and mass spectrometry (MS) was carried out with Q Exactive manufactured by Thermo Fisher Scientific K.K.

In the LC separation, a given column was used at a column temperature of 40° C., and solution sending was performed in such a manner that an appropriate solvent was selected, the sample was prepared by dissolving [Ir(tBuppm)₂(4dppy)] in an organic solvent at an arbitrary concentration, and the injection amount was 5.0 μL.

In the MS analysis, a component with m/z=845.31, which is an ion derived from [Ir(tBuppm)₂(4dppy)] was measured by a Targeted-MS² method. For Targeted-MS², the mass range was set to ±2.0 m/z and detection was performed in a positive mode. Energy for accelerating an ion (normalized collision energy: NCE) was set to 30 for the measurement. The obtained MS spectrum is shown in FIG. 45.

FIG. 45 shows that product ions of [Ir(tBuppm)₂(4dppy)] are mainly detected around m/z=634 and 615. The results in FIG. 45 show characteristics derived from [Ir(tBuppm)₂(4dppy)] and therefore can be regarded as important data for identifying [Ir(tBuppm)₂(4dppy)] contained in a mixture.

It can be presumed that the product ion around m/z=634 is a cation in a state where HtBuppm (abbreviation) is eliminated from [Ir(tBuppm)₂(4dppy)]. This suggests that [Ir(tBuppm)₂(4dppy)] contains tBuppm (abbreviation). It can be presumed that the product ion around m/z=615 is a cation in a state where H4dppy (abbreviation) is eliminated from [Ir(tBuppm)₂(4dppy)]. This suggests that [Ir(tBuppm)₂(4dppy)] contains H4dppy (abbreviation).

Example 9 Synthesis Example 6

In this example is described a method for synthesizing the organometallic complex of one embodiment of the present invention, bis{2-[4-phenyl-2-(1,3,5-triadinyl)-κN]phenyl-κC}[2-(2-pyridinyl-κN)phenyl-κC]iridium(III) (abbreviation: [Ir(dptzn)₂(ppy)]) which is represented by Structural Formula (200) in Embodiment 1. A structure of [Ir(dptzn)₂(ppy)] is shown below.

Synthesis of bis{2-[4-phenyl-2-(1,3,5-triadinyl)-κN]phenyl-κC}[2-(2-pyridinyl-κN)phenyl-KC] iridium(III) (abbreviation: [Ir(dptzn)₂(ppy)]

First, 2.5 g (2.3 mmol) of di-μ-chloro-tetrakis[2-(2-pyridinyl-κN)phenyl-KC]diiridium(III) (abbreviation: [Ir(ppy)₂Cl]₂) and 400 mL of dichloromethane were put into a 1000 mL three-neck flask and stirred under a nitrogen stream.

To this mixed solution were dripped a mixed solution of 1.8 g (6.9 mmol) of silver trifluoromethanesulfonate and 120 mL of methanol, and the mixed solution was stirred for 17 hours in a dark place. After the reaction for the predetermined time, the reaction mixture was filtered through Celite. The obtained filtrate was concentrated to give 3.7 g of a yellow solid. Then, 3.7 g of the obtained solid, 100 mL of 1-butanol, and 2.1 g (9.2 mmol) of 2,6-diphenyl-1,3,5-triazine (abbreviation: Hdptzn) were put into a 300 mL recovery flask and were heated and refluxed under a nitrogen stream for 35 hours.

After the reaction for the predetermined time, the reaction mixture was concentrated to give a solid. Dichloromethane was added to the obtained solid, and the mixture was filtered through a filter aid in which Celite, neutral silica, and Celite were stacked in this order. The obtained filtrate was concentrated to give a solid. The obtained solid was purified by silica column chromatography. As developing solvents, first, a 2:1 hexane-dichloromethane mixed solvent was used, and then a 3:4 hexane-dichloromethane mixed solvent was used. A fraction of the obtained substance was concentrated to give a solid. The obtained solid was recrystallized from ethyl acetate/ethanol to give 0.19 g of an orange solid in a yield of 5%. The synthesis scheme is shown in (f) below.

Analysis results by nuclear magnetic resonance (¹H-NMR) spectroscopy of the orange solid obtained in the above-described synthesis method are shown below. FIG. 46 shows the ¹H-NMR chart. These results reveal that the organometallic complex [Ir(dptzn)₂(ppy)] represented by Structural Formula (200) was obtained in this synthesis example.

¹H-NMR δ (CDCl₃): 6.81-7.04 (m, 10H), 7.51-7.60 (m, 6H), 7.70-7.71 (m, 2H), 7.85 (d, 1H), 7.95 (d, 1H), 8.21 (s, 1H), 8.37 (t, 2H), 8.50 (s, 1H), 8.55 (d, 2H), 8.58 (d, 2H).

Next, an ultraviolet-visible absorption spectrum (hereinafter, simply referred to as an “absorption spectrum”) of a dichloromethane solution of [Ir(dptzn)₂(ppy)] and an emission spectrum thereof were measured. The measurement of the absorption spectrum was conducted at room temperature, for which an ultraviolet and visible spectrophotometer (V550 type manufactured by JASCO Corporation) was used and the dichloromethane solution (0.0123 mmol/L) was put in a quartz cell. In addition, the measurement of the emission spectrum was conducted at room temperature, for which an absolute PL quantum yield measurement system (C11347-01 manufactured by Hamamatsu Photonics K.K.) was used and the deoxidized dichloromethane solution (0.0123 mmol/L) was sealed in a quartz cell under a nitrogen atmosphere in a glove box (LABstar M13 (1250/780) manufactured by Bright Co., Ltd.). Measurement results of the obtained absorption and emission spectra are shown in FIG. 47, in which the horizontal axis represents wavelength and the vertical axes represent absorption intensity and emission intensity. Note that the absorption spectrum in FIG. 47 is the results obtained in such a way that the absorbance measured by putting only dichloromethane in a quartz cell was subtracted from the absorbance measured by putting the dichloromethane solution (0.0123 mmol/L) in a quartz cell.

As shown in FIG. 47, the organometallic complex [Ir(dptzn)₂(ppy)] has an emission peak at 631 nm, and red light emission was observed from dichloromethane.

Next, [Ir(dptzn)₂(ppy)] obtained in this example was subjected to analysis by liquid chromatography-mass spectrometry (LC-MS).

In the LC-MS analysis, liquid chromatography (LC) separation was carried out with UltiMate 3000 manufactured by Thermo Fisher Scientific K.K., and mass spectrometry (MS) was carried out with Q Exactive manufactured by Thermo Fisher Scientific K.K.

In the LC separation, a given column was used at a column temperature of 40° C., and solution sending was performed in such a manner that an appropriate solvent was selected, the sample was prepared by dissolving [Ir(dptzn)₂(ppy)] in an organic solvent at an arbitrary concentration, and the injection amount was 5.0 μL.

In the MS analysis, a component with m/z of 812.21, which is an ion derived from [Ir(dptzn)₂(ppy)], was measured by a Targeted-MS² method. For Targeted-MS², the mass range was set to ±2.0 m/z and detection was performed in a positive mode. Energy for accelerating an ion (normalized collision energy: NCE) was set to 30 for the measurement. The obtained MS spectrum is shown in FIG. 48.

FIG. 48 shows that product ions of [Ir(dptzn)₂(ppy)] are mainly detected around m/z=656 and 579. The results in FIG. 48 show characteristics derived from [Ir(dptzn)₂(ppy)] and therefore can be regarded as important data for identifying [Ir(dptzn)₂(ppy)] contained in a mixture.

It can be presumed that the product ion around m/z=656 is a cation in a state where phenylpyridine (abbreviation: Hppy) is eliminated from [Ir(dptzn)₂(ppy)]. It can be presumed that the product ion around m/z=579 is a cation in a state where Hdptzn (abbreviation) is eliminated from [Ir(dptzn)₂(ppy)]. These suggest that [Ir(dptzn)₂(ppy)] contains Hppy (abbreviation) and Hdptzn (abbreviation).

Example 10 Synthesis Example 7

In this example is described a method for synthesizing the organometallic complex of one embodiment of the present invention, {2-[4-phenyl-2-(1,3,5-triadinyl)-κN]phenyl-κC}bis[2-(2-pyridinyl-κN)phenyl-κC]iridium(III) (abbreviation: [Ir(ppy)₂(dptzn)]) which is represented by Structural Formula (300) in Embodiment 1. A structure of [Ir(ppy)₂(dptzn)] is shown below.

Synthesis of {2-[4-phenyl-2-(1,3,5-triadinyl)-κN]phenyl-κC}bis[2-(2-pyridinyl-κN)phenyl-KC]iridium(III) (abbreviation: [Ir(ppy)₂(dptzn)]

First, 2.5 g (2.3 mmol) of di-μ-chloro-tetrakis[2-(2-pyridinyl-κN)phenyl-κC]diiridium(III) (abbreviation: [Ir(ppy)₂Cl]₂) and 400 mL of dichloromethane were put into a 1000 mL three-neck flask and stirred under a nitrogen stream. To this mixed solution were dripped a mixed solution of 1.8 g (6.9 mmol) of silver trifluoromethanesulfonate and 120 mL of methanol, and the mixed solution was stirred for 17 hours in a dark place.

After the reaction for the predetermined time, the reaction mixture was filtered through Celite. The obtained filtrate was concentrated to give 3.7 g of a yellow solid. Then, 3.7 g of the obtained solid, 100 mL of 1-butanol, and 2.1 g (9.2 mmol) of 2,6-diphenyl-1,3,5-triazine (abbreviation: Hdptzn) were put into a 300 mL recovery flask and were heated and refluxed under a nitrogen stream for 35 hours. After the reaction for the predetermined time, the reaction mixture was concentrated to give a solid.

Dichloromethane was added to the obtained solid, and the mixture was filtered through a filter aid in which Celite, neutral silica, and Celite were stacked in this order. The obtained filtrate was concentrated to give a solid. The obtained solid was purified by silica column chromatography. As developing solvents, first, a 2:1 hexane-dichloromethane mixed solvent was used, and then a 3:4 hexane-dichloromethane mixed solvent was used. A fraction of the obtained substance was concentrated to give a solid. The obtained solid was recrystallized from ethyl acetate/ethanol to give 0.11 g of an orange solid in a yield of 3%. The synthesis scheme is shown in (g) below.

Analysis results by nuclear magnetic resonance (¹H-NMR) spectroscopy of the orange solid obtained in the above-described synthesis method are shown below. FIG. 49 shows the ¹H-NMR chart. These results reveal that the organometallic complex [Ir(ppy)₂(dptzn)] represented by Structural Formula (300) was obtained in this synthesis example.

¹H-NMR δ (CDCl₃): 6.80-7.00 (m, 11H), 7.50-7.70 (m, 8H), 7.81 (d, 1H), 7.90-7.94 (m, 2H), 8.20 (s, 1H), 8.33-8.35 (m, 1H), 8.56 (d, 2H).

Next, an ultraviolet-visible absorption spectrum (hereinafter, simply referred to as an “absorption spectrum”) of a dichloromethane solution of [Ir(ppy)₂(dptzn)] and an emission spectrum thereof were measured. The measurement of the absorption spectrum was conducted at room temperature, for which an ultraviolet and visible spectrophotometer (V550 type manufactured by JASCO Corporation) was used and the dichloromethane solution (0.0192 mmol/L) was put in a quartz cell. In addition, the measurement of the emission spectrum was conducted at room temperature, for which an absolute PL quantum yield measurement system (C11347-01 manufactured by Hamamatsu Photonics K.K.) was used and the deoxidized dichloromethane solution (0.0192 mmol/L) was sealed in a quartz cell under a nitrogen atmosphere in a glove box (LABstar M13 (1250/780) manufactured by Bright Co., Ltd.). Measurement results of the obtained absorption and emission spectra are shown in FIG. 50, in which the horizontal axis represents wavelength and the vertical axes represent absorption intensity and emission intensity. Note that the absorption spectrum in FIG. 50 is the results obtained in such a way that the absorbance measured by putting only dichloromethane in a quartz cell was subtracted from the absorbance measured by putting the dichloromethane solution (0.0192 mmol/L) in a quartz cell.

As shown in FIG. 50, the organometallic complex [Ir(ppy)₂(dptzn)] has an emission peak at 663 nm, and red light emission was observed from dichloromethane.

Next, [Ir(ppy)₂(dptzn)] obtained in this example was subjected to analysis by liquid chromatography-mass spectrometry (LC-MS).

In the LC-MS analysis, liquid chromatography (LC) separation was carried out with UltiMate 3000 manufactured by Thermo Fisher Scientific K.K., and mass spectrometry (MS) was carried out with Q Exactive manufactured by Thermo Fisher Scientific K.K.

In the LC separation, a given column was used at a column temperature of 40° C., and solution sending was performed in such a manner that an appropriate solvent was selected, the sample was prepared by dissolving [Ir(ppy)₂(dptzn)] in an organic solvent at an arbitrary concentration, and the injection amount was 5.0 μL.

In the MS analysis, a component with m/z of 734.19, which is an ion derived from [Ir(ppy)₂(dptzn)], was measured by a Targeted-MS² method. For Targeted-MS², the mass range was set to ±2.0 m/z and detection was performed in a positive mode. Energy for accelerating an ion (normalized collision energy: NCE) was set to 30 for the measurement. The obtained MS spectrum is shown in FIG. 51.

FIG. 51 shows that product ions of [Ir(ppy)₂(dptzn)] are mainly detected around m/z=579 and 501. The results in FIG. 51 show characteristics derived from [Ir(ppy)₂(dptzn)] and therefore can be regarded as important data for identifying [Ir(ppy)₂(dptzn)] contained in a mixture.

It can be presumed that the product ion around m/z=579 is a cation in a state where phenylpyridine (abbreviation: Hppy) is eliminated from [Ir(ppy)₂(dptzn)]. It can be presumed that the product ion around m/z=501 is a cation in a state where Hdptzn (abbreviation) is eliminated from [Ir(ppy)₂(dptzn)]. These suggest that [Ir(ppy)₂(dptzn)] contains Hppy (abbreviation) and Hdptzn (abbreviation).

Example 11 Synthesis Example 8

In this example is described a method for synthesizing the organometallic complex, bis[2-(4,5-dimethyl-2-pyridinyl-κK)phenyl-κC][2-(6-phenyl-4-pyrimidinyl-κN³)phenyl-κC]iridium(III) (abbreviation: [Ir(dppm)(dmppy)₂]) which is represented by Structural Formula (118) in Embodiment 1. A structure of [Ir(dppm)(dmppy)₂] is shown below.

Step 1: Synthesis of 5-bromo-4-methyl-2-phenylpyridine

First, 15 g (60 mmol) of 2,5-dibromo-4-methyl-2-phenylpyridine, 7.3 g (60 mmol) of phenylboronic acid, 3.0 g (22 mmol) of potassium carbonate, 380 mL of toluene, and 38 mL of water were put into a 1000 mL three-neck flask. Then, the atmosphere in the flask was replaced with nitrogen, and the mixture was degassed by being stirred while the pressure in the flask was reduced. After that, the atmosphere in the flask was replaced with nitrogen, and 3.5 g (3.0 mmol) of tetrakis(triphenylphosphine)palladium(0) was added to the mixture. The mixture was stirred at 110° C. for 16 hours under a nitrogen stream.

Water was added to the obtained reaction solution to separate the solution into an organic layer and an aqueous layer, and the aqueous layer was subjected to extraction with toluene. The organic layer and the obtained solution of the extract were combined, and washed with saturated saline. Then, anhydrous magnesium sulfate was added to the solution for drying. The obtained mixture was subjected to gravity filtration, and the filtrate was concentrated to give an oily substance. The obtained oily substance was purified by silica column chromatography. As the developing solvent, a 12:1 hexane-ethyl acetate mixed solvent was used. A fraction of the obtained substance was concentrated to give 13 g of a colorless oily substance. The obtained oily substance was a mixture of a target substance and the source material, 2,5-dibromo-4-methyl-2-phenylpyridine. Therefore, the reaction was repeated two more times to give 6.2 g of the colorless oily target substance in a yield of 42%. The obtained colorless oily substance was identified as 5-bromo-4-methyl-2-phenylpyridine by nuclear magnetic resonance (NMR) spectroscopy. The synthesis scheme of Step 1 is shown in (h-1) below.

Step 2: Synthesis of 4,5-dimethyl-2-phenylpyridine (abbreviation: Hdmppy)

Next, 6.2 g (25 mmol) of 5-bromo-4-methyl-2-phenylpyridine synthesized in Step 1, 5.2 g (41 mmol) of trimethylboroxine, 1.0 g (2.5 mmol) of 2-dicyclohexylphosphino-2′,6′-dimethoxybiphenyl (S-phos), 8.0 g (38 mmol) of tripotassium phosphate, 180 mL of toluene, and 18 mL of water were put into a 500 mL three-neck flask. Then, the atmosphere in the flask was replaced with nitrogen, and the mixture was degassed by being stirred while the pressure in the flask was reduced. After that, the atmosphere in the flask was replaced with nitrogen, and 0.46 g (0.5 mmol) of tris(dibenzylideneacetone)dipalladium(0) was added to the mixture. The mixture was stirred at 110° C. for 23 hours under a nitrogen stream.

Water was added to the obtained reaction solution to separate the solution into an organic layer and an aqueous layer, and the aqueous layer was subjected to extraction with toluene. The organic layer and the obtained solution of the extract were combined, and washed with saturated saline. Then, anhydrous magnesium sulfate was added to the organic layer for drying. The obtained mixture was subjected to gravity filtration, and the filtrate was concentrated to give an oily substance. The obtained oily substance was purified by silica column chromatography. As the developing solvent, a 20:1 hexane-ethyl acetate mixed solvent was used. A fraction of the obtained substance was concentrated to give 4.5 g of a yellow oily substance in a yield of 98%. The obtained yellow oily substance was identified as 4,5-dimethyl-2-phenylpyridine (abbreviation: Hdmppy) by nuclear magnetic resonance (NMR) spectroscopy. The synthesis scheme of Step 2 is shown in (h-2) below.

Step 3: Synthesis of bis[2-(4,5-dimethyl-2-pyridinyl-κN²)phenyl-κC][2-(6-phenyl-4-pyrimidinyl-κN³)phenyl-κC]iridium(III) (abbreviation: [Ir(dppm)(dmppy)₂])

Next, 2.1 g (1.5 mmol) of di-μ-chloro-tetrakis[2-(6-phenyl-4-pyrimidinyl-κN³)phenyl-κC]diiridium(III) (abbreviation: [Ir(dppm)₂Cl]₂) and 300 mL of dichloromethane were put into a 1000 mL three-neck flask and stirred under a nitrogen stream. To this mixed solution was dripped a mixed solution of 1.2 g (4.5 mmol) of silver trifluoromethanesulfonate and 150 mL of methanol, and the mixed solution was stirred for 16 hours in a dark place.

After the reaction for the predetermined time, the reaction mixture was filtered through Celite. The obtained filtrate was concentrated to give 2.8 g of a reddish brown solid. Then, 2.8 g of the obtained solid, 30 mL of ethanol, 30 mL of methanol, and 1.1 g (6.0 mmol) of 4,5-dimethyl-2-phenylpyridine (abbreviation: Hdmppy) synthesized in Step 2 were put into a 500 mL recovery flask and were heated and refluxed under a nitrogen stream for 32 hours. After the reaction for the predetermined time, the reaction mixture was concentrated to give a solid. Dichloromethane was added to the obtained solid, and the mixture was filtered through a filter aid in which Celite, neutral silica gel, and Celite were stacked in this order.

The obtained filtrate was concentrated, and the obtained oily substance was purified by silica column chromatography. As the developing solvent, a 2:1 hexane-dichloromethane mixed solvent was used. A fraction of the obtained substance was concentrated to give a solid. This solid was recrystallized from ethyl acetate/hexane to give 0.18 g of a red solid in a yield of 8%. By a train sublimation method, 0.18 g of the obtained solid was purified by heating at 280° C. for 21 hours under a pressure of 2.6 Pa with an argon flow rate of 5.0 mL/min After the sublimation purification, 0.10 g of a red solid which was a target substance was obtained at a collection rate of 56%. The synthesis scheme of Step 3 is shown in (h-3) below.

Analysis results by nuclear magnetic resonance (¹H-NMR) spectroscopy of the target substance (red solid) obtained in Step 3 are shown below. FIG. 52 shows the ¹H-NMR chart. These results reveal that the organometallic complex [Ir(dppm)(dmppy)₂] represented by Structural Formula (118) was obtained in this synthesis example.

¹H-NMR δ (CDCl₃): 2.01 (s, 3H), 2.03 (s, 3H), 2.32 (s, 3H), 2.33 (s, 3H), 6.72 (d, 1H), 6.79-6.96 (m, 8H), 7.27 (s, 1H), 7.36 (s, 1H), 7.47-7.53 (m, 3H), 7.60-7.66 (m, 4H), 7.85 (d, 1H), 8.07 (d, 2H), 8.16 (d, 1H), 8.25 (d, 1H).

Next, an ultraviolet-visible absorption spectrum (hereinafter, simply referred to as an “absorption spectrum”) of a dichloromethane solution of [Ir(dppm)(dmppy)₂] and an emission spectrum thereof were measured. The measurement of the absorption spectrum was conducted at room temperature, for which an ultraviolet and visible spectrophotometer (V550 type manufactured by JASCO Corporation) was used and the dichloromethane solution (0.0152 mmol/L) was put in a quartz cell. In addition, the measurement of the emission spectrum was conducted at room temperature, for which an absolute PL quantum yield measurement system (C11347-01 manufactured by Hamamatsu Photonics K.K.) was used and the deoxidized dichloromethane solution (0.0152 mmol/L) was sealed in a quartz cell under a nitrogen atmosphere in a glove box (LABstar M13 (1250/780) manufactured by Bright Co., Ltd.). Measurement results of the obtained absorption and emission spectra are shown in FIG. 53, in which the horizontal axis represents wavelength and the vertical axes represent absorption intensity and emission intensity. In FIG. 53, two solid lines are shown; a thin line represents the absorption spectrum, and a thick line represents the emission spectrum. The absorption spectrum in FIG. 53 is the results obtained in such a way that the absorbance measured by putting only dichloromethane in a quartz cell was subtracted from the absorbance measured by putting the dichloromethane solution (0.0152 mmol/L) in a quartz cell.

As shown in FIG. 53, the organometallic complex [Ir(dppm)(dmppy)₂] has an emission peak at 629 nm, and red light emission was observed from dichloromethane.

Example 12 Synthesis Example 9

In this example is described a method for synthesizing the organometallic complex, {2-[6-(1,1-dimethylethyl)-4-pyrimidinyl-κN³]phenyl-κC}bis[2-(4-phenyl-2-pyridinyl-κN)phenyl-κC]iridium(III) (abbreviation: [Ir(tBuppm)(4dppy)₂]) which is represented by Structural Formula (119) in Embodiment 1. A structure of [Ir(tBuppm)(4dppy)₂] is shown below.

First, 3.5 g of [Ir(4dppy)₂Cl]₂ (abbreviation) and 250 mL of dichloromethane were put into a three-neck flask, and the atmosphere in the flask was replaced with nitrogen. A mixed solution of 2.0 g of silver triflate and 30 mL of methanol was dripped into the flask, followed by stirring for 20 hours at room temperature. The obtained reaction product was filtered through Celite. The filtrate was concentrated to give a solid. Then, 2.9 g of HtBuppm (abbreviation), 50 mL of 2-ethoxyethanol, and 50 mL of N,N-dimethylformamide (abbreviation: DMF) were added to the solid, and the mixture was refluxed in a nitrogen atmosphere for 15 hours.

The obtained mixture was concentrated to give a solid. The obtained solid was purified by neutral silica gel column chromatography using chloroform and hexane in a ratio of 2:3 as a developing solvent. Further purification was performed by neutral silica gel column chromatography using dichloromethane and hexane in a ratio of 1:1 as a developing solvent. The obtained solution was concentrated, followed by recrystallization from dichloromethane and methanol to give the organometallic complex [Ir(tBuppm)(4dppy)₂] as an orange solid (yield: 27%).

By a train sublimation method, 0.12 g of the obtained orange solid was purified under a pressure of 2.7 Pa with an argon flow rate of 5 mL/min at 305° C. After the sublimation purification, an orange solid which was a target substance was obtained in a yield of 59%. The synthesis scheme of the above synthesis method is shown in (i) below.

Analysis results by nuclear magnetic resonance (¹H-NMR) spectroscopy of the orange solid obtained by the above-described synthesis method are shown below. FIG. 54 shows the ¹H-NMR chart. These results reveal that the organometallic complex [Ir(tBuppm)(4dppy)₂] represented by Structural Formula (119) was obtained in this synthesis example.

¹H-NMR δ (CDCl₃): 1.38 (s, 9H), 6.84 (d, 1H), 6.87-6.97 (m, 8H), 7.07 (dd, 1H), 7.16 (dd, 1H), 7.42-7.51 (m, 6H), 7.60 (d, 2H), 7.66-7.67 (m, 4H), 7.76-7.80 (m, 4H), 8.05 (ds, 1H), 8.10 (ds, 1H), 8.26 (ds, 1H). Note that a peak at around 5.29 derives from dichloromethane.

Next, an ultraviolet-visible absorption spectrum (hereinafter, simply referred to as an “absorption spectrum”) of a deoxidized dichloromethane solution of [Ir(tBuppm)(4dppy)₂] and an emission spectrum thereof were measured. The measurement of the absorption spectrum was conducted at room temperature, for which an ultraviolet and visible spectrophotometer (V550 type manufactured by JASCO Corporation) was used and the dichloromethane solution (0.019 mmol/L) was put in a quartz cell. In addition, the measurement of the emission spectrum was conducted at room temperature, for which an absolute PL quantum yield measurement system (C11347-01 manufactured by Hamamatsu Photonics K.K.) was used and the deoxidized dichloromethane solution (0.019 mmol/L) was sealed in a quartz cell under a nitrogen atmosphere in a glove box (LABstar M13 (1250/780) manufactured by Bright Co., Ltd.).

Measurement results of the obtained absorption and emission spectra are shown in FIG. 55, in which the horizontal axis represents wavelength and the vertical axes represent absorption intensity and emission intensity. In FIG. 55, two solid lines are shown; a thin line represents the absorption spectrum, and a thick line represents the emission spectrum. The absorption spectrum in FIG. 55 is the results obtained in such a way that the absorbance measured by putting only dichloromethane in a quartz cell was subtracted from the absorbance measured by putting the dichloromethane solution (0.019 mmol/L) in a quartz cell.

As shown in FIG. 55, the organometallic complex [Ir(tBuppm)(4dppy)₂] has an emission peak at 563 nm, and yellow light emission was observed from the dichloromethane solution.

Next, [Ir(tBuppm)(4dppy)₂] obtained in this example was subjected to a mass spectrometry (MS) analysis by liquid chromatography-mass spectrometry (LC-MS).

In the LC-MS analysis, liquid chromatography (LC) separation was carried out with UltiMate 3000 manufactured by Thermo Fisher Scientific K.K., and mass spectrometry (MS) was carried out with Q Exactive manufactured by Thermo Fisher Scientific K.K.

In the LC separation, a given column was used at a column temperature of 40° C., and solution sending was performed in such a manner that an appropriate solvent was selected, the sample was prepared by dissolving [Ir(tBuppm)(4dppy)₂] in an organic solvent at an arbitrary concentration, and the injection amount was 5.0 μL.

In the MS analysis, a component with m/z of 864.28, which is an ion derived from [Ir(tBuppm)(4dppy)₂], was measured by a Targeted-MS² method. For Targeted-MS², the mass range was set to ±2.0 m/z and detection was performed in a positive mode. Energy for accelerating an ion (normalized collision energy: NCE) was set to 40 for the measurement. The obtained MS spectrum is shown in FIG. 56.

FIG. 56 shows that product ions of [Ir(tBuppm)(4dppy)₂] are mainly detected around m/z=653 and 634. The results in FIG. 56 show characteristics derived from [Ir(tBuppm)(4dppy)₂] and therefore can be regarded as important data for identifying [Ir(tBuppm)(4dppy)₂] contained in a mixture.

It can be presumed that the product ion around m/z=653 is a cation in a state where tBuppm (abbreviation) is eliminated from [Ir(tBuppm)(4dppy)₂]. This suggests that [Ir(tBuppm)(4dppy)₂] contains HtBuppm (abbreviation). It can be presumed that the product ion around m/z=634 is a cation in a state where 4dppy (abbreviation) is eliminated from [Ir(tBuppm)(4dppy)₂]. This suggests that [Ir(tBuppm)(4dppy)₂] contains H4dppy (abbreviation).

Example 13

In this example, as light-emitting elements of one embodiment of the present invention, a light-emitting element 6 including, in a light-emitting layer, [Ir(dppm)₂(dmppy)] (114) whose synthesis method is described as one example in Example 3 and a light-emitting element 7 including, in a light-emitting layer, [Ir(dppm)(dmppy)₂] (118) whose synthesis method is described as one example in Example 11 were fabricated. The measurement results of the characteristics of these light-emitting elements are shown. Note that in this example, the methods for fabricating the light-emitting elements 6 and 7 are the same as those described in Example 5 except that some different materials are used, and the description is omitted here. Chemical formulae of materials used in this example are shown below.

<<Fabrication of Light-Emitting Elements 6 and 7>>

Table 6 shows the element structures of the light-emitting element 6 and the light-emitting element 7 fabricated in this example

TABLE 6 Hole- Hole- Light- Electron- First injection transport emitting injection Second electrode layer layer layer Electron-transport layer layer electrode Light-emitting ITO DBT3P-II: BPAFLP * 2mDBTBPDBq-II BPhen LiF Al element 6 (70 nm) MoOx (20 nm) (20 nm) (10 nm) (1 nm) (200 nm) (42, 60 nm) Light-emitting ITO DBT3P-II: BPAFLP ** 2mDBTBPDBq-II BPhen LiF Al element 7 (70 nm) MoOx (20 nm) (20 nm) (10 nm) (1 nm) (200 nm) (42, 60 nm) *2mDBTBPDBq-II:PCBBiF:[Ir(dppm)₂(mdppy)] (0.7:0.30.05 (20 nm)\0.8:0.2:0.05 (20 nm)) **2mDBTBPDBq-II:PCBBiF:[Ir(dppm)(mdppy)₂] (0.70.30.05 (20 nm)\0.8:0.2:0.05 (20 nm))

<<Operation Characteristics of Light-Emitting Elements 6 and 7>>

Next, operation characteristics of the light-emitting elements were measured. Note that the measurement was carried out at room temperature (in an atmosphere where a temperature was maintained at 25° C.).

FIG. 57, FIG. 58, FIG. 59, and FIG. 60 show current density-luminance characteristics, voltage-luminance characteristics, luminance-current efficiency characteristics, and voltage-current characteristics, respectively, of the light-emitting elements 6 and 7.

Table 7 shows initial values of main characteristics of the light-emitting elements at around 1000 cd/m².

TABLE 7 Current Current Power External Voltage Current density Chromaticity Luminance efficieincy efficiency quantum (V) (mA) (mA/cm²) (x, y) (cd/m²) (cd/A) (1 m/W) efficiency (%) Light-emitting 2.9 0.10 2.5 (0.61, 0.39) 1000 40 43 22 element 6 Light-emitting 2.8 0.12 3.1 (0.61, 0.39) 1000 33 37 18 element 7

FIG. 61 shows emission spectra of the light-emitting elements to which current was applied at a current density of 2.5 mA/cm². In FIG. 61, each of the emission spectra of the light-emitting elements 6 and 7 has a peak at around 605 nm, which presumably derives from red-orange light emission of [Ir(dppm)₂(dmppy)] that is the organometallic complex used for the EL layer of the light-emitting element 6 and [Ir(dppm)(dmppy)₂] that is the organometallic complex used for the EL layer of the light-emitting element 7.

Next, reliability tests were performed on the light-emitting elements. FIG. 62 shows results of the reliability tests. In FIG. 62, the vertical axis represents normalized luminance (%) with an initial luminance of 100%, and the horizontal axis represents driving time (h) of the elements. As the reliability tests, driving tests at a constant current of 2 mA were performed.

The results shown in FIG. 62 reveal that each of the light-emitting elements 6 and 7 including the organometallic complexes of one embodiment of the present invention has high reliability. A probable reason for this is that the organometallic complex of one embodiment of the present invention has a shallow HOMO and a deep LUMO as a whole because the HOMO and the LUMO are spatially separated from each other by being distributed over different ligands. In other words, in each of the organometallic complexes used as the light-emitting materials in the light-emitting elements 6 and 7, both at the time of carrier transport and in an excited state, holes are distributed over a ligand that is highly resistant to holes (the first ligand over which the HOMO is likely to be distributed), and electrons are distributed over a ligand that is highly resistant to electrons (the second ligand over which the LUMO is likely to be distributed). This probably makes it possible to increase stability at the time of carrier transport and in an excited state and to manufacture a light-emitting element with long lifetime. Furthermore, by such separation of the HOMO and the LUMO from each other, the organometallic complex itself can transport both carriers; thus, carrier balance can be adjusted and a recombination region in the light-emitting layer can be prevented from becoming narrow in a light-emitting element manufactured using this organometallic complex. This can also be considered a factor for achieving an increase of lifetime.

In the light-emitting element 7 fabricated using the organometallic complex with two dmppy ligands and one dppm ligand, the effect of increasing lifetime is particularly significant. This indicates that the presence of two ligands over which the HOMO is distributed and one ligand over which the LUMO is distributed is important in terms of an increase in lifetime. That is, an organometallic complex is more stable when including more ligands capable of accepting holes.

Example 14

In this example, as light-emitting elements of one embodiment of the present invention, a light-emitting element 8 including, in a light-emitting layer, [Ir(tBuppm)₂(4dppy)] (117) whose synthesis method is described as one example in Example 8 and a light-emitting element 9 including, in a light-emitting layer, [Ir(tBuppm)(4dppy)₂] (119) whose synthesis method is described as one example in Example 12 were fabricated. The measurement results of the characteristics of these light-emitting elements are shown. Note that in this example, the methods for fabricating the light-emitting elements 8 and 9 are the same as those described in Example 5 except that some different materials are used, and the description is omitted here. Chemical formulae of materials used in this example are shown below.

<<Fabrication of Light-Emitting Elements 8 and 9>>

Table 8 shows the element structures of the light-emitting element 8 and the light-emitting element 9 fabricated in this example

TABLE 8 Hole- Hole- Light- Electron- First injection transport emitting injection Second electrode layer layer layer Electron-transport layer layer electrode Light-emitting ITO DBT3P-II: BPAFLP * 2mDBTBPDBq-II BPhen LiF Al element 8 (70 nm) MoOx (20 nm) (7.8 nm) (20 nm) (1 nm) (200 nm) (1:0.5, 60 nm) Light-emitting ITO DBT3P-II: BPAFLP ** 2mDBTBPDBq-II BPhen LiF Al element 9 (70 nm) MoOx (20 nm) (7.8 nm) (20 nm) (1 nm) (200 nm) (1:0.5, 60 nm) *2mDBTBPDBq-II:PCBBiF:[Ir(tBuppm)₂(4dppy)] (0.7:0.3:0.075 (20 nm)\0.8:0.2:0.075 (20 nm)) **2mDBTBPDBq-II:PCBBiF:[Ir(tBuppm)(4dppy)₂] (0.7:0.3:0.075 (20 nm)\0.8:0.2:0.075 (20 nm))

<<Operation Characteristics of Light-Emitting Elements 8 and 9>>

Next, operation characteristics of the light-emitting elements were measured. Note that the measurement was carried out at room temperature (in an atmosphere where a temperature was maintained at 25° C.).

FIG. 63, FIG. 64, FIG. 65, and FIG. 66 show current density-luminance characteristics, voltage-luminance characteristics, luminance-current efficiency characteristics, and voltage-current characteristics, respectively, of the light-emitting elements 8 and 9.

Table 9 shows initial values of main characteristics of the light-emitting elements at around 1000 cd/m².

TABLE 9 Current Current Power External Voltage Current density Chromaticity Luminance efficieincy efficiency quantum (V) (mA) (mA/cm²) (x, y) (cd/m²) (cd/A) (1 m/W) efficiency (%) Light-emitting 2.7 0.037 0.92 (0.41, 0.57) 750 81 95 22 element 8 Light-emitting 2.8 0.060 1.5 (0.45, 0.54) 940 62 70 18 element 9

FIG. 67 shows emission spectra of the light-emitting elements to which current was applied at a current density of 2.5 mA/cm². In FIG. 67, each of the emission spectra of the light-emitting elements 8 and 9 has a peak at around 605 nm, which presumably derives from yellow light emission of [Ir(tBuppm)₂(4dppy)] that is the organometallic complex used for the EL layer of the light-emitting element 8 and [Ir(tBuppm)(4dppy)₂] that is the organometallic complex used for the EL layer of the light-emitting element 9.

Next, reliability tests were performed on the light-emitting elements. FIG. 68 shows results of the reliability tests. In FIG. 68, the vertical axis represents normalized luminance (%) with an initial luminance of 100%, and the horizontal axis represents driving time (h) of the elements. As the reliability tests, driving tests at a constant current of 2 mA were performed.

The results shown in FIG. 68 reveal that each of the light-emitting elements 8 and 9 including the organometallic complexes of one embodiment of the present invention has high reliability. A probable reason for this is that the organometallic complex of one embodiment of the present invention has a shallow HOMO and a deep LUMO as a whole because the HOMO and the LUMO are spatially separated from each other by being distributed over different ligands. In other words, in each of the organometallic complexes used as the light-emitting materials in the light-emitting elements 8 and 9, both at the time of carrier transport and in an excited state, holes are distributed over a ligand that is highly resistant to holes (the first ligand over which the HOMO is likely to be distributed), and electrons are distributed over a ligand that is highly resistant to electrons (the second ligand over which the LUMO is likely to be distributed). This probably makes it possible to increase stability at the time of carrier transport and in an excited state and to manufacture a light-emitting element with long lifetime. Furthermore, by such separation of the HOMO and the LUMO from each other, the organometallic complex itself can transport both carriers; thus, carrier balance can be adjusted and a recombination region in the light-emitting layer can be prevented from becoming narrow in a light-emitting element manufactured using this organometallic complex. This can also be considered a factor for achieving an increase of lifetime.

In the light-emitting element 9 fabricated using the organometallic complex with two 4dppy ligands and one tBuppm ligand, the effect of increasing lifetime is particularly significant. This indicates that the presence of two ligands over which the HOMO is distributed and one ligand over which the LUMO is distributed is important in terms of an increase in lifetime. That is, an organometallic complex is more stable when including more ligands capable of accepting holes.

EXPLANATION OF REFERENCE

101: first electrode, 102: EL layer, 103: second electrode, 111: hole-injection layer, 112: hole-transport layer, 113: light-emitting layer, 114: electron-transport layer, 115: electron-injection layer, 201: first electrode, 202(1): first EL layer, 202(2): second EL layer, 202(n−1): (n−1)-th EL layer, 202(n): n-th EL layer, 204: second electrode, 205: charge-generation layer, 205(1): first charge-generation layer, 205(2): second charge-generation layer, 205(n−2): (n−2)-th charge-generation layer, 205 (n−1): (n−1)-th charge-generation layer, 301: element substrate, 302: pixel portion, 303: driver circuit portion (source line driver circuit), 304 a, 304 b: driver circuit portion (gate line driver circuit), 305: sealant, 306: sealing substrate, 307: wiring, 308: flexible printed circuit (FPC), 309: FET, 310: FET, 312: current control FET, 313 a, 313 b: first electrode (anode), 314: insulator, 315: EL layer, 316: second electrode (cathode), 317 a, 317 b: light-emitting element, 318: space, 320 a, 320 b: conductive film, 321, 322: region, 323: lead wiring, 324: coloring layer (color filter), 325: black layer (black matrix), 326, 327, 328: FET, 401: substrate, 402: first electrode, 403 a, 403 b, 403 c: EL layer, 404: second electrode, 405: light-emitting element, 406: insulating film, 407: partition, 900: substrate, 901: first electrode, 902: EL layer, 903: second electrode, 911: hole-injection layer, 912: hole-transport layer, 913: light-emitting layer, 914: electron-transport layer, 915: electron-injection layer, 2000: touch panel, 2000′: touch panel, 2501: display panel, 2502R: pixel, 2502 t: transistor, 2503 c: capacitor, 2503 g: scan line driver circuit, 2503 t: transistor, 2509: FPC, 2510: substrate, 2511: wiring, 2519: terminal, 2521: insulating layer, 2528: insulator, 2550R: light-emitting element, 2560: sealing layer, 2567BM: light-blocking layer, 2567 p: anti-reflection layer, 2567R: coloring layer, 2570: substrate, 2590: substrate, 2591: electrode, 2592: electrode, 2593: insulating layer, 2594: wiring, 2595: touch sensor, 2597: adhesive layer, 2598: wiring, 2599: terminal, 2601: pulse voltage output circuit, 2602: current sensing circuit, 2603: capacitor, 2611: transistor, 2612: transistor, 2613: transistor, 2621: electrode, 2622: electrode, 3200: substrate, 3201: cathode, 3202: EL layer, 3203: anode, 3213: light-emitting layer, 3214: electron-injection layer, 3215: hole-transport layer, 3216: hole-injection layer, 3217: insulator, 3300: head portion, 3301 a: spraying portion, 3301 c: spraying portion, 3302 a: piezoelectric element, 3302 c: piezoelectric element, 3303 a: ink, 3303 c: ink, 4000: lighting device, 4001: substrate, 4002: light-emitting element, 4003: substrate, 4004: electrode, 4005: EL layer, 4006: electrode, 4007: electrode, 4008: electrode, 4009: auxiliary wiring, 4010: insulating layer, 4011: sealing substrate, 4012: sealant, 4013: desiccant, 4015: diffusion plate, 4100: lighting device, 4200: lighting device, 4201: substrate, 4202: light-emitting element, 4204: electrode, 4205: EL layer, 4206: electrode, 4207: electrode, 4208: electrode, 4209: auxiliary wiring, 4210: insulating layer, 4211: sealing substrate, 4212: sealant, 4213: barrier film, 4214: planarization film, 4215: diffusion plate, 4300: lighting device, 5101: light, 5102: wheel, 5103: door, 5104: display portion, 5105: steering wheel, 5106: gear lever, 5107: seat, 5108: inner rearview mirror, 7100: television device, 7101: housing, 7103: display portion, 7105: stand, 7107: display portion, 7109: operation key, 7110: remote controller, 7201: main body, 7202: housing, 7203: display portion, 7204: keyboard, 7205: external connection port, 7206: pointing device, 7302: housing, 7304: display portion, 7305: icon indicating time, 7306: another icon, 7311: operation button, 7312: operation button, 7313: connection terminal, 7321: band, 7322: clasp, 7400: cellular phone, 7401: housing, 7402: display portion, 7403: operation button, 7404: external connection portion, 7405: speaker, 7406: microphone, 7407: camera, 7500(1), 7500(2): housing, 7501(1), 7501(2): first screen, 7502(1), 7502(2): second screen, 8001: lighting device, 8002: lighting device, 8003: lighting device, 9310: portable information terminal, 9311: display portion, 9312: display region, 9313: hinge, and 9315: housing.

This application is based on Japanese Patent Application serial No. 2016-074489 filed with Japan Patent Office on Apr. 1, 2016, the entire contents of which are hereby incorporated by reference. 

1. (canceled)
 2. An organometallic complex having a structure represented by General Formula (G1):

wherein R¹ to R⁵ and R⁷ to R¹⁵ separately represent hydrogen, an alkyl group having 1 to 6 carbon atoms, an unsubstituted aryl group having 6 to 13 carbon atoms, or an unsubstituted heteroaryl group having 3 to 12 carbon atoms, wherein R⁶ represents a tert-butyl group, and wherein light emission of the organometallic complex is yellow.
 3. The organometallic complex according to claim 2, wherein the structure is represented by any one of (100), (102), and (117):


4. The organometallic complex according to claim 2, wherein the organometallic complex is included in a light-emitting layer.
 5. The organometallic complex according to claim 4, wherein the organometallic complex is included in the light-emitting layer with a first organic compound and a second organic compound.
 6. The organometallic complex according to claim 5, wherein the first organic compound and the second organic compound form an exciplex.
 7. An organometallic complex comprises: a first ligand comprising a phenylpyridine ligand and a second ligand comprising a ligand of a phenylpyrimidine derivative represented by General Formula (G1):

wherein R¹ to R⁵ and R⁷ to R¹⁵ separately represent hydrogen, an alkyl group having 1 to 6 carbon atoms, an unsubstituted aryl group having 6 to 13 carbon atoms, or an unsubstituted heteroaryl group having 3 to 12 carbon atoms, wherein R⁶ represents a tert-butyl group, wherein a HOMO is distributed over the first ligand, and wherein a LUMO is distributed over the second ligand.
 8. The organometallic complex according to claim 7, wherein the organometallic complex is represented by any one of (100), (102), and (117):


9. The organometallic complex according to claim 7, wherein the organometallic complex is included in a light-emitting layer.
 10. The organometallic complex according to claim 9, wherein the organometallic complex is included in the light-emitting layer with a first organic compound and a second organic compound.
 11. The organometallic complex according to claim 10, wherein the first organic compound and the second organic compound form an exciplex.
 12. The organometallic complex according to claim 7, wherein light emission of the organometallic complex is yellow. 